CN106590886A - Complex calcium-based lubricating grease and preparing method thereof - Google Patents
Complex calcium-based lubricating grease and preparing method thereof Download PDFInfo
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Abstract
The invention provides a complex calcium-based lubricating grease and a preparing method thereof. The lubricating grease comprises 0.01%-1.0% of hindered phenol compound, 5%-35% of complex calcium-based thickening agent and a main amount of lubricating base oil, wherein the structure of the hindered phenol compound is shown in the specifications. According to the complex calcium-based lubricating grease and the preparing method thereof, the complex calcium-based lubricating grease has a high dropping point, good mechanical stability, excellent heat stability, colloid stability, high-temperature oxygen resistance, anti-corrosion performance, anti-water spraying performance, and anti-extreme pressure performance, hardening conditions of the complex calcium-based lubricating grease are improved to some extent, thus the complex calcium-based lubricating grease is capable of being qualified in lubrication of various kinds of motors, electric generators, air blowers, transportation industries, iron and steel enterprises and other various kinds of commercial units, and is especially applicable to lubrication of friction parts of various kinds of mechanical equipment under high-temperature and moist conditions.
Description
Technical field
The present invention relates to a kind of grease, more particularly to a kind of complex calcium lubricating grease.
Background technology
Complex calcium lubricating grease is a kind of earliest complex soap lubricating grease of development, and it is to use fatty acid calcium soap
Moderately viscous mineral lubricating oil or synthetic lubricant fluid are thickened with calcium complex soap made by low molecular acid calcium salt
Made by grease product, be a kind of broad-spectrum grease using wider range.But by
There are problems that hardening during storage and use in complex calcium lubricating grease, it promotes big with application limited
System.
It is in recent years the performance for improving complex calcium lubricating grease, have is carried out on formula and manufacturing process to it
Improved, such as CN 1888036A and CN 101935573A is by small molecule acid and long chain organic acid
The selection of species and the adjustment of ratio, and from some small molecules acid (boric acid) and other adminiclies (two
Titanium oxide) improving the hardening problem of complex calcium lubricating grease, but the production time is oversize and hardening improves journey
Degree is limited；Also have by introducing polyurea grease to be improved its performance, such as CN 1493673A,
US 5084193 and US 4902435, complex calcium lubricating grease is mixed with polyureas base grease, but raw
Produce raw material complex with technique.CN 101921651A are made by adding surfactant in formula
It forms synergism with soap molecule, and then improves the arrangement mode of soap molecule and the ability of solidification base oil
So as to improve the Surface hardened layer performance of complex calcium lubricating grease.
Grease keeps its property that permanent change does not occur in storage with the effect of air is resisted when using
Ability be referred to as oxidation stability, be the weight that causes grease oxidation deterioration as the metal soap of thickening agent
Want reason.In order to suppress the oxidation deterioration of grease, anti-oxidation product to cause the corrosion of metal surface,
Add appropriate antioxidant additive.At present, conventional antioxidant is broadly divided into amine and the class of phenols two.
Phenolic antioxidant generally comprises 2,6 ditertiary butyl p cresol, 2,6- di-tert-butylphenols etc., but it uses temperature
Degree is relatively low, typically within 150 DEG C.Amine antioxidants are mainly alkylated diphenylamine, or alkylation
Phenyl-naphthylamines etc..Existing antioxidant yet suffers from room for improvement on high temperature antioxygen property.
The content of the invention
The invention provides a kind of complex calcium lubricating grease and preparation method thereof.
Content of the present invention including the following aspects：
1. a kind of complex calcium lubricating grease, on the basis of grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the composite calcium-base thickening agent and major amount of lubrication base of 5%-35%
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, and is each independently selected from hydrogen, C1-300Directly
Chain or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
It is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III), 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, each independent
Ground is selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight or branched
Alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other, each
It is independently groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain
Or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched alkane
Base and C3-10Straight or branched miscellaneous alkyl；Each group R2It is same to each other or different to each other, is each independently selected from
Hydrogen, C1-20Group and the group shown in logical formula V shown in straight or branched alkyl, logical formula (IV)
(preferably it is each independently selected from hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV))；
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Straight or branched alkyl is (excellent
Choosing is each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group RcIt is same to each other or different to each other,
It is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl epoxide is (preferably
It is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, it is more excellent
Choosing is in cyclic groupThe para-position of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；
Z is 0 to 3 integer (preferably 0 or 1)；N is 1 to 8 integer (preferably 1 or 2)；N' is 0
To 7 integer (preferably 0,1 or 2), on condition that n'+n≤8 (preferred n'+n=1 or n'+n=2)；Respectively
Group RdIt is same to each other or different to each other, is each independently selected from hydrogen and the group shown in logical formula V (preferably
Hydrogen)；Each 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), wherein two adjacent cyclic groupsEach other optionally by additional S atom and bridge
Connect the N atoms of the two rings and form phenothiazine ring, and/or, two adjacent cyclic groups
Each other optionally by additional group(wherein group R " it is selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10Directly
Chain 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, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
It is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III) (preferably each solely
On the spot selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' is same to each other or different to each other, each independent
Ground is selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight or branched
Alkyl)；Group L is groupWherein group R " 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, C1-10Straight chain
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 selected from inside straight or branched alkyl molecular structure
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- be selected from
(R' is H or C for-O- ,-S- and-NR'-1-4Straight or branched alkyl) one of substituting group directly replace
Generation and obtain group and straight or branched alkyl molecular structure inside one or more (such as 1 to 3
It is individual, 1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining,
The wherein shielding phenolic compounds at least one group R in its whole molecular structuredIt is hydrogen.
2., according to the shielding phenolic compounds described in any preceding aspect, following materialization is preferably selected from
The mixture of compound or its arbitrary proportion：
3. the preparation method of aforementioned shielding phenolic compounds, including the phenolic compounds made shown in logical formula (X)
With the amines shown in formula (Y) in the aldehyde compound (preferred formaldehyde) shown in formula (Z)
In the presence of the first step that reacts, optionally also include making product and the sulfuration of the first step
Agent (preferred sulfur) is reacted and/or attached with aldehyde compound (preferred formaldehyde) reaction shown in formula (Z)
Plus step,
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from hydrogen ,-SH
And C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is polyolefin-based for 300-3000's), on condition that at least one group R0It is-SH；Each group R' that
This is identical or different, is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably independently of one another
Selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Directly
Chain or branched alkyl (are preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group Rc
It is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain is propped up
Alkyl group epoxide (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight chain is propped up
Alkyl group epoxide, is more preferably in cyclic groupThe para-position 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)；Each cyclic groupIt is same to each other or different to each other, is each independently selected from phenyl ring
With naphthalene nucleus (preferred phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl)
And C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight chain
Or branched heteroalkyl groups,
Wherein, the straight or branched miscellaneous alkyl is selected from inside straight or branched alkyl molecular structure
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- be selected from
(R' is H or C for-O- ,-S- and-NR'-1-4Straight or branched alkyl) one of substituting group directly replace
Generation and obtain group and straight or branched alkyl molecular structure inside one or more (such as 1 to 3
It is individual, 1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining.
4. according to the preparation method of the shielding phenolic compounds described in any preceding aspect, wherein described the
In one step, the phenolic compounds shown in the logical formula (X) and the amine compounds shown in the formula (Y)
The mol ratio of thing is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, the logical formula (X) institute
The phenolic compounds for showing are 1 with the mol ratio of the aldehyde compound shown in the formula (Z):0.1-10, preferably
1:0.5-5.0, more preferably 1:0.8-2.0, the amination in the additional step, shown in the formula (Y)
Compound is 1 with the mol ratio of the vulcanizing agent:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0, institute
State the amines shown in formula (Y) is with the mol ratio of the aldehyde compound shown in the formula (Z)
1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
5. the complex calcium lubricating grease described in any preceding aspect, the shielding phenolic compounds account for described multiple
Close the 0.01%-10%, preferred 0.05%-5% of calcium base grease composition gross weight.
The composite calcium-base thickening agent of the present invention can be generated by acid with calcium hydroxide reaction, and the acid is height
Molecule is sour, the mixed acid of the acid of middle molecule and low molecular acid, the polymer acid be C12-C25 fatty acids and
/ or hydroxy fatty acid, can be the one kind in lauric acid, Palmic acid, stearic acid and 12- hydroxy stearic acids
Or various, preferred stearic acid and/or 12- hydroxy stearic acids；The middle molecule acid can be C6-C10 carboxylics
One or more in acid, preferably octanoic acid, benzoic acid, p-phthalic acid, Azelaic Acid, decanedioic acid；
The low molecular acid be C2-C5 carboxylic acids, preferred acetic acid.The polymer acid mol ratio sour with middle molecule
Preferably 0.37-3.4：1；The molal quantity of the low molecular acid and polymer acid, middle molecule acid molal quantity it
The ratio of sum is preferably 0.9-4：1.
The lubricating base oil can be one or more in mineral oil, vegetable oil and artificial oil, preferably
100 DEG C of kinematic viscositys are 5-60mm2The lubricating base oil of/s, most preferably 10-30mm2The lubrication base of/s
Oil.The vegetable oil can be one or more in Oleum Ricini, Oleum Brassicae campestriss, Oleum Arachidis hypogaeae semen and Oleum Glycines.Institute
It can be one or more in poly-a-olefin oil (PAO), Esters oil, fluorocarbon oil and silicone oil to state artificial oil.
Various additives, such as extreme pressure anti-wear additives, antirust agent can also be contained in grease of the present invention.Its
In, extreme pressure anti-wear additives account for the 0.5%-12% of grease gross weight, preferred 0.5%-5%, can be two sulfur
For Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formate, three
It is phenyl phosphorothioate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, politef, thio
Molybdenum phosphate, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorination
At least one in graphite, Calcium Carbonate and Zinc Oxide；Antirust agent accounts for the 0.01%-4.5% of grease gross weight,
It is preferred that 0.1%-2%, can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole,
At least one in zinc naphthenate and alkenyl succinic acid.
In the present invention, the content of each component is calculated according to inventory in grease composition.Wherein,
Content=100% of the composite calcium-base thickening agent × (weight of the weight of polymer acid calcium+middle molecule acid calcium+low
The weight of molecule acid calcium)/grease gross weight.
The invention provides a kind of preparation method of complex calcium lubricating grease, including：Composite calcium-base is thickened
Agent and lubricating base oil mix homogeneously, in 180-230 DEG C of constant temperature refining, are cooled to 100-130 DEG C, add
Foregoing shielding phenolic compounds, grind to form fat.
The preparation method of the preferred complex calcium lubricating grease of the present invention, including：
It is anti-by saponification is carried out at normal temperatures with low molecular acid after partial lubrication base oil and calcium hydroxide mixing
Should, when temperature rises to 80-100 DEG C, add polymer acid to carry out saponification, after reaction completely, plus
Entering middle molecule acid carries out saponification, is warming up to 200-220 DEG C after reaction completely and is refined, Ran Houjia
Enter remaining lubricating base oil and be cooled to 100-130 DEG C, add foregoing shielding phenolic compounds, grind
Wear into fat.
Wherein, the calcium hydroxide is preferred 15-50 DEG C with the reaction temperature of low molecular acid, with low molecular acid
Carry out the time preferred 1-60 minutes of saponification, more preferably 10-30 minutes；Carry out with middle molecule acid
The time of saponification is preferably 5-60 minutes, more preferably 20-40 minutes；Soap is carried out with polymer acid
Change the time preferred 10-120 minutes of reaction, more preferably 30-90 minutes.
The weight of the partial lubrication base oil and remaining lubricating base oil is than preferred 50-75：25-50.
The polymer acid is preferably 0.37-3.4 with the mol ratio of middle molecule acid：1；The low molecular acid
Molal quantity and polymer acid, the ratio of middle molecule acid molal quantity sum are preferably 0.9-4：1.
The mol ratio of polymer acid, the total amount of the acid of middle molecule and low molecular acid and calcium hydroxide is preferably and completes
The equivalent ratio of saponification, the wherein amount of calcium hydroxide can also excess 1-10 weight %.
The refining temperature is preferred 200-220 DEG C, refining time preferred 5-20 minutes.
The complex calcium lubricating grease of the present invention has higher dropping point, good mechanical stability, excellent
Heat stability, colloid stability, high temperature antioxidant, rustless property, anti-water drenching energy and extreme pressure property,
And also having a certain degree of improvement to its sclerotic conditions so that the fat can be competent in various motors, generating
The lubrication of machine, aerator, transportation, iron and steel enterprise and other various industrial equipments, it is particularly suitable
The lubrication of the friction part of plant equipment under various higher temperature wet conditions.
Specific embodiment
In the complex calcium lubricating grease of the present invention, it is related to the shielding phenolate shown in a kind of logical formula (I) and closes
Thing.
According to the present invention, in logical formula (I), when having multiple, each group R is mutually the same or not
Together, hydrogen, C are each independently selected from1-300Group shown in straight or branched alkyl, logical formula (II) and logical
Group shown in formula (III), on condition that at least one group R is the group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Straight or branched alkyl, such as may be used
To enumerate C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more preferably C1-4Straight chain
Or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically can such as enumerate number and divide equally
Son amount Mn is the polyolefin-based of 300-3000.Now, as the polyolefin-based number-average molecular weight
Mn, more preferably preferred 500-2000,500-1500.It is described polyolefin-based (basic according to the present invention
On) it is saturation (being rendered as chain alkyl structure), but depending on as the polyolefinic of initiation material
It is likely to containing a small amount of in the difference of species or the process for preparing polyolefins, the polyolefin-based strand
Olefinic double bond (is remained such as in polyolefin manufacturing process or introduced), but this has no effect on the present invention
The realization of effect, the present invention also has no intention to carry out clearly the amount, and the present invention is still by this polyene
Alkyl is classified as " alkyl ".
, in logical formula (I), there are multiple group R, wherein one in an embodiment of the invention
Individual group R is the group shown in logical formula (II), and in two other group R is the polyolefin
Base, another is hydrogen, C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl) or formula
(III) group shown in.
An embodiment of the invention, in logical formula (I), when group R is the polyolefin
During base, the polyolefin-based para-position 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' is mutually the same or not
Together, hydrogen and C are each independently selected from1-20Straight 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 alkyl.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " selected from hydrogen,
C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in logical formula (II), in the definition of group L, base
Group R " 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 alkyl,
The group shown in group and logical formula V shown in logical formula (IV).
An embodiment of the invention, in logical formula (II), group R2Selected from hydrogen, C1-10
Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (II), when having multiple, each group RbIt is mutually the same or not
Together, hydrogen and C are each independently selected from1-20Straight or branched alkyl, be preferably each independently 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 alkyl, preferred hydrogen.
According to the present invention, in logical formula (II), when having multiple, each group RcIt is mutually the same or not
Together, hydrogen, C are each independently selected from1-20Straight or branched alkyl and C1-20Straight 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 alkyl and C1-10Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in logical formula (II), preferably one group RcIn ring
GroupUpper N atoms are (that is, with group RdThe N atoms of bonding) para-position.
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 RdIt is mutually the same or not
Together, hydrogen and the group shown in logical formula V, preferred hydrogen are each independently selected from.
According to the present invention, in logical formula (II), when having multiple, each cyclic group(
The inside configuration of logical formula (II) is rendered as divalent group) it is same to each other or different to each other, it is each independently selected from
Phenyl ring (inside configuration preferably in logical formula (II) is rendered as 1,4- phenylenes) and naphthalene nucleus are (preferably logical
The inside configuration of formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (II), two adjacent cyclic groupsAdditional S atom (not showing in structural formula) and bridge joint the two rings can be passed through each other
N atoms (that is, with group RdThe N atoms of bonding) and form phenothiazine ring, i.e.,
, in logical formula (II), there is plural cyclic group in the embodiment of the inventionWhen, as long as wherein at least two (adjacent) cyclic groupForm the fen thiophene
Piperazine ring, it is not necessary that require these cyclic groupsIn each is another with adjacent
Individual cyclic groupForm the phenothiazine ring.
An embodiment of the invention, in logical formula (II), two adjacent cyclic groupsAdditional group can be passed through each other(not showing in structural formula) and bridge joint
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and 9,10- acridan rings are formed,
I.e.
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " selected from hydrogen and
C1-10Straight or branched alkyl.
, in logical formula (II), there is plural cyclic group in the embodiment of the inventionWhen, as long as wherein at least two (adjacent) cyclic groupForm the 9,10-
Acridan ring, it is not necessary that require these cyclic groupsIn each with it is adjacent
Another cyclic groupForm the acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " selected from hydrogen,
C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in logical formula (III), in the definition of group L, base
Group R " 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 or branched alkyl,
The group shown in group and logical formula V shown in logical formula (IV).
An embodiment of the invention, in logical formula (III), group R2Selected from hydrogen, C1-10
Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (III), when having multiple, each group RbIt is mutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl, be 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 alkyl, preferred hydrogen.
According to the present invention, in logical formula (III), when having multiple, each group RcIt is mutually the same or
Difference, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight 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 alkyl and C1-10Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in logical formula (III), preferably one group RcIt is in
Cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) para-position.
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 RdIt is mutually the same or
Difference, 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(
The inside configuration of logical formula (III) is rendered as divalent group) it is same to each other or different to each other, it is each independently selected from
Phenyl ring (inside configuration preferably in logical formula (III) is rendered as 1,4- phenylenes) and naphthalene nucleus are (preferably logical
The inside configuration of formula (III) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (III), two adjacent cyclic groupsAdditional S atom (not showing in structural formula) and bridge joint the two rings can be passed through each other
N atoms (that is, with group RdThe N atoms of bonding) and form phenothiazine ring, i.e.,
, in logical formula (III), there is plural ring group in the embodiment of the invention
GroupWhen, as long as wherein at least two (adjacent) cyclic groupForm the fen
Thiazine ring, it is not necessary that require these cyclic groupsIn each is another with adjacent
One cyclic groupForm the phenothiazine ring.
An embodiment of the invention, in logical formula (III), two adjacent cyclic groupsAdditional group can be passed through each other(not showing in structural formula) and bridge joint
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and 9,10- acridan rings are formed,
I.e.
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " selected from hydrogen and
C1-10Straight or branched alkyl.
, in logical formula (III), there is plural ring group in the embodiment of the invention
GroupWhen, as long as wherein at least two (adjacent) cyclic groupForm described
9,10- acridan rings, it is not necessary that require these cyclic groupsIn each with
Another adjacent cyclic groupForm the acridan ring.
According to the present invention, in logical formula (IV), when having multiple, each group RbIt is mutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl, be 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 alkyl, preferred hydrogen.
According to the present invention, in logical formula (IV), when having multiple, each group RcIt is mutually the same or
Difference, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight 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 alkyl and C1-10Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in logical formula (IV), preferably one group RcIt is in
Cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) para-position.
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, and preferably 0,1 or 2 are front
It is n'+n≤8 to carry.An embodiment of the invention, n'+n=1 or n'+n=2.Here, n with it is front
The definition stated in logical formula (II) is identical.
According to the present invention, in logical formula (IV), when having multiple, each group RdIt is mutually the same or
Difference, 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(
The inside configuration of logical formula (IV) is rendered as divalent group) it is same to each other or different to each other, it is each independently selected from
Phenyl ring (inside configuration preferably in logical formula (IV) is rendered as 1,4- phenylenes) and naphthalene nucleus are (preferably logical
The inside configuration of formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (IV), two adjacent cyclic groupsAdditional S atom (not showing in structural formula) and bridge joint the two rings can be passed through each other
N atoms (that is, with group RdThe N atoms of bonding) and form phenothiazine ring, i.e.,
, in logical formula (IV), there is plural ring group in the embodiment of the invention
GroupWhen, as long as wherein at least two (adjacent) cyclic groupForm the fen
Thiazine ring, it is not necessary that require these cyclic groupsIn each is another with adjacent
One cyclic groupForm the phenothiazine ring.
An embodiment of the invention, in logical formula (IV), two adjacent cyclic groupsAdditional group can be passed through each other(not showing in structural formula) and bridge joint
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and 9,10- acridan rings are formed,
I.e.
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " selected from hydrogen and
C1-10Straight or branched alkyl.
, in logical formula (IV), there is plural ring group in the embodiment of the invention
GroupWhen, as long as wherein at least two (adjacent) cyclic groupForm described
9,10- acridan rings, it is not necessary that require these cyclic groupsIn each with
Another adjacent cyclic groupForm the acridan ring.
According to the present invention, in logical formula V, when having multiple, each group R is mutually the same or not
Together, hydrogen, C are each independently selected from1-300Group shown in straight or branched alkyl, logical formula (II) and logical
Group shown in 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 alkyl.
According to the present invention, in logical formula V, as the C1-300Straight or branched alkyl, such as may be used
To enumerate C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more preferably C1-4Straight chain
Or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically can such as enumerate number and divide equally
Son amount Mn is the polyolefin-based of 300-3000.Now, as the polyolefin-based number-average molecular weight
Mn, more preferably preferred 500-2000,500-1500.It is described polyolefin-based (basic according to the present invention
On) it is saturation (being rendered as chain alkyl structure), but depending on as the polyolefinic of initiation material
It is likely to containing a small amount of in the difference of species or the process for preparing polyolefins, the polyolefin-based strand
Olefinic double bond (is remained such as in polyolefin manufacturing process or introduced), but this has no effect on the present invention
The realization of effect, the present invention also has no intention to carry out clearly the amount, and the present invention is still by this polyene
Alkyl is classified as " alkyl ".
, in logical formula V, there are multiple group R in an embodiment of the invention, wherein
One group R is described polyolefin-based, and another is hydrogen or C1-20Straight or branched alkyl is (preferably
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 the polyolefin
During base, the polyolefin-based para-position 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' is mutually the same or not
Together, hydrogen and C are each independently selected from1-20Straight 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 alkyl.
According to the present invention, in logical formula V, group L is group
According to the present invention, in logical formula V, in the definition of group L, group R " selected from hydrogen,
C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in logical formula V, in the definition of group L, base
Group R " 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, in the definition of group L,
Group R " is 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- is occupied respectively
Three positions of residue in logical formula V on phenyl ring.
According to the present invention, in logical formula V, a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds define 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 the present invention
One is preferred embodiment, it is described shielding phenolic compounds in its whole molecular structure comprising at most 5,
At most 3, at most 2 or at most 1 phenol unit.
According to the present invention, the shielding phenolic compounds define 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 structureMake
For amine unit.According to one preferred embodiment of the invention, the shielding phenolic compounds entirely divide at it
In minor structure comprising at most 15, at most 10, at most 8, at most 6, at most 4, extremely
Many 3 or at most 2 amine units.
According to the present invention, the shielding phenolic compounds preferably at least have one in its whole molecular structure
(preferably 2,3 or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolate
Compound is preferably in its whole molecular structure containing selected from following hydrogen amine unit (1), hydrogen amine unit (2)
At least one of with hydrogen amine unit (3).In these hydrogen amine units, cyclic groupAnd base
Group R " is identical with the definition in logical formula (II).
A preferred implementation of the invention, the shielding phenolic compounds are in its whole molecular structure
In contain hydrogen amine unit (1) described at least one.
Specifically, shielding phenolic compoundsAs a example by, the compound is whole at its
Comprising 2 phenol units and 2 amine units in molecular structure, and comprising 1 hydrogen amine list
First (1).
According to the present invention, as the shielding phenolic compounds, such as can enumerate following compound or
The mixture of its arbitrary proportion, but the present invention is not limited to this.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be with single one kind (pure)
In the form of compound, manufacture or use, it is also possible to (press and appoint with the mixture of wherein two or more
Meaning ratio) in the form of, manufacture or use, this has no effect on the realization of effect of the present invention.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be by following preparation
Method is manufactured, but is not limited to this sometimes.
Preparation method of the invention, including the phenolic compounds and formula that make shown in logical formula (X)
(Y) amines shown in react in the presence of the aldehyde compound shown in formula (Z)
One step.
According to the present invention, in leading to formula (X), when having multiple, each group R0It is same to each other or different to each other,
It is each independently selected from hydrogen ,-SH and C1-300Straight or branched alkyl, on condition that at least one group R0
It is-SH.
According to the present invention, in logical formula (X), as the C1-300Straight or branched alkyl, such as may be used
To enumerate C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more preferably C1-4Straight chain
Or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically can such as enumerate number and divide equally
Son amount Mn is the polyolefin-based of 300-3000.Now, as the polyolefin-based number-average molecular weight
Mn, more preferably preferred 500-2000,500-1500.It is described polyolefin-based (basic according to the present invention
On) it is saturation (being rendered as chain alkyl structure), but depending on as the polyolefinic of initiation material
It is likely to containing a small amount of in the difference of species or the process for preparing polyolefins, the polyolefin-based strand
Olefinic double bond (is remained such as in polyolefin manufacturing process or introduced), but this has no effect on the present invention
The realization of effect, the present invention also has no intention to carry out clearly the amount, and the present invention is still by this polyene
Alkyl is classified as " alkyl ".
, in logical formula (X), there are multiple group R in an embodiment of the invention0, wherein
One group R0It is-SH, two other group R0In one be 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 the polyolefin
During base, the polyolefin-based para-position 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' is mutually the same or not
Together, hydrogen and C are each independently selected from1-20Straight 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 alkyl.
According to the present invention, as the phenolic compounds shown in the logical formula (X), can directly using commercially available
Product, it is also possible to manufactured by conventionally known in the art method, be not particularly limited.
In addition, as the phenolic compounds shown in the logical formula (X), can only using one kind, it is also possible to two kinds
Or multiple combination is used.
According to the present invention, as the preparation method of the phenolic compounds shown in the logical formula (X), such as may be used
To enumerate in the presence of catalyst for alkylation reaction, the phenolic compounds and polyolefin shown in formula (X') are made
There is alkyl in (number-average molecular weight Mn is 300-3000, more preferably preferred 500-2000,500-1500)
The method for changing reaction.
According to the present invention, in formula (X'), group R' has and identical in aforementioned formula (X)
Implication.
According to three group R' of presence in the present invention, formula (X')0, one of group R'0It is-SH,
Another group R'0It is H, the 3rd group R'0It is hydrogen ,-SH or C1-20Straight or branched alkyl is (excellent
Select 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 para-position of phenolic hydroxyl group in formula (X').
According to the present invention, the polyolefin preferably passes through ethylene, propylene or C4-C10The homopolymerization of alpha-olefin or
Person is by polyolefin obtained from two or more copolymerization in these alkene.As the C4-C10α-alkene
Hydrocarbon, 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
Polymer chain 70wt%) contains olefinic double bond in its end.The olefinic double bond is usually to be lived with high reaction
In the form of the ethenylidene or vinyl of property.
According to the present invention, as the polyolefin, more preferably polybutene.Unless otherwise stated, this paper institutes
The term " polybutene " for using broadly includes the polymer by obtained from 1-butylene or isobutylene homopolymerisation, with
And by two or three in 1-butylene, 2-butylene and isobutene. by copolymerization obtained polymer.This
The birds of the same feather flock together commercially available prod of compound is likely to other olefinic components containing negligible quantity, but this has no effect on this
The enforcement of invention.
According to the present invention, used as the polyolefin, further preferred polyisobutylene (PIB) is also referred to as high
Activity polyisobutylene.In this kind of polyisobutylene, and at least 20wt% (preferably at least 50wt%, more
Preferably at least 70wt%) total terminal ethylenic double bond provided by methyl ethenylidene.
As the catalyst for alkylation reaction, such as Lewis acid catalysts can be enumerated, such as be selected from
Aluminum chloride, boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol
One or more in complex and boron trifluoride ether complex, wherein it is preferred that boron trifluoride diethyl etherate complexation
Thing and/or boron trifluoride methanol complex.These catalyst for alkylation reaction can directly using commercially available
Product.
According to the present invention, in the alkylated reaction, shown in the polyolefin, the formula (X')
Phenolic compounds, the catalyst for alkylation reaction between mol ratio such as can be 1：1-3：0.1-0.5,
It is preferred that 1：1.5-3：0.1-0.4, most preferably 1：1.5-3：0.2-0.4, but this is not limited to sometimes.
According to the present invention, the response time of the alkylated reaction is such as 0.5h-10h, preferred 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, preferably 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 the solvent,
C can such as be enumerated6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein,
Hexane and heptane are preferably used, more preferably using hexane.
It is anti-from what is finally obtained by conventional methods after the alkylated reaction terminates according to the present invention
Answer remove in mixture catalyst for alkylation reaction, unreacted reactant and the solvent that may use it
Afterwards, that is, the phenolic compounds shown in the logical formula (X) are obtained.
According to the present invention, in formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl
And group
According to the present invention, in formula (Y), when having multiple, each group RbIt is mutually the same or not
Together, hydrogen and C are each independently selected from1-20Straight or branched alkyl, be preferably each independently 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 alkyl, preferred hydrogen.
According to the present invention, in formula (Y), when having multiple, each group RcIt is mutually the same or not
Together, hydrogen, C are each independently selected from1-20Straight or branched alkyl and C1-20Straight 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 alkyl and C1-10Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in formula (Y), preferably one group RcIn ring
GroupUpper N atoms are (that is, with group RdThe N atoms of bonding) para-position.
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(
The inside configuration of formula (Y) is rendered as divalent group) it is same to each other or different to each other, it is each independently selected from
Phenyl ring (inside configuration preferably in formula (Y) is rendered as 1,4- phenylenes) and naphthalene nucleus are (preferably logical
The inside configuration of formula (Y) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), wherein it is preferred that phenyl ring.
According to the present invention, as the amines shown in the formula (Y), can directly using commercially available
Product, be not particularly limited.In addition, as the amines shown in the formula (Y),
Can only using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20
Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in formula (Z), group R " it is selected from hydrogen, C1-10
Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to one preferred embodiment of the invention, in formula (Z), group R " selected from hydrogen and
C1-10Straight or branched alkyl.
According to the present invention, as the aldehyde compound shown in the formula (Z), such as C can be enumerated1-6
Aliphatic aldehyde and benzaldehyde.
An embodiment of the invention, as the C1-6Aliphatic aldehyde, such as can enumerate
C1-6Straight or branched saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably formaldehyde.As described
Formaldehyde, such as can use its aqueous solution, paraformaldehyde or paraformaldehyde form, particularly not limit
It is fixed.
According to the present invention, as the aldehyde compound shown in the formula (Z), one kind can be only used,
Can also combination of two or more use.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step,
The mol ratio of the phenolic compounds shown in the logical formula (X) and the amines shown in the formula (Y)
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,
The mol ratio of the phenolic compounds shown in the logical formula (X) and the aldehyde compound shown in the formula (Z)
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 be
Carry out in the presence of solvent.As the solvent, such as can enumerate C2-10Aliphatic nitrile (such as acetonitrile
Deng), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as just oneself
Alkane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as methanol, ethanol, normal propyl alcohol, isopropanol,
N-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- bis-
Chlorobenzene), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as two
Methylformamide, dimethyl acetylamide and N-Methyl pyrrolidone) etc..These solvents can be used only
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,
Catalyst can be added without, it is also possible to add catalyst.As the catalyst, such as can enumerate nothing
Machine acid catalyst and organic acid catalyst.As the inorganic acid catalyst, such as can enumerate hydrochloric acid,
Sulphuric acid and phosphoric acid etc..As the organic acid catalyst, such as can enumerate pyrovinic acid, ethylsulfonic acid,
Sulfamic acid and p-methyl benzenesulfonic acid etc..
As the consumption of the catalyst, can be directly with reference to the conventional amount used of prior art not special
Other restriction.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the anti-of the first step
There is no particular limitation between seasonable, but generally 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 anti-of the first step
There is no particular limitation to answer temperature, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C
-120℃。
According to the present invention, in the preparation method of the shielding phenolic compounds, terminate in the first step
Afterwards, the reaction for being obtained from the first step by conventionally known separation method (such as evaporation etc.) is mixed
The volatility things such as solvent that may be present are removed in compound (the hereinafter referred to as reactant mixture of first step)
After matter, you can obtain the product of first step.
An embodiment of the invention, the preparation method of the shielding phenolic compounds optionally also includes
Make the product of the first step and vulcanizing agent reaction (forming phenothiazine ring) additional step (with
It is referred to as additional step A down).
An embodiment of the invention, the preparation method of the shielding phenolic compounds optionally also includes
The product of the first step is set (to form 9,10- with the aldehyde compound reaction shown in aforementioned formula (Z)
Acridan ring) additional step (hereinafter referred to as additional step B).
According to the present invention, in the preparation method of the shielding phenolic compounds, can only carry out described additional
Step A, it is also possible to only carry out the additional step B, it is also possible to not only carried out the additional step A but also entered
The row additional step B.When carrying out the additional step B the additional step A is not only carried out,
To the precedence of the additional step A and the additional step B, there is no particular limitation, Ke Yixian
The additional step A is carried out, the additional step B is carried out again after additional step A terminates, or
Person first carries out the additional step B, and after additional step B terminates the additional step A is carried out again.
In addition, can have product (that is, from the product of previous additional step) point between each additional step
From step, it is also possible to there is no product separating step, be not particularly limited.
An embodiment of the invention, it is described in the preparation method of the shielding phenolic compounds
Additional step A is carried out after the first step terminates.Now, the product of the first step
Separate from the reactant mixture of the first step as previously mentioned.Or, the first step
Rapid product can also be without the separation, and directly with the reactant mixture of the first step
Form is used to carry out the additional step A.Or, the additional step A can also be in the extra step
Rapid B is carried out after terminating.When the additional step A after the additional step B terminates when carrying out,
The product reaction from the additional step B as described herein of the additional step B mixes
Separate in thing.Or, the product of the additional step B can also without the separation, and
Directly it is used to carry out the additional step A in the form of the reactant mixture of the additional step B.
An embodiment of the invention, in the preparation method of the shielding phenolic compounds, in institute
In stating additional step A, as the vulcanizing agent, such as sulfur and sulfur dichloride etc. can be enumerated, wherein excellent
Select sulfur.As the sulfur, such as can enumerate sulfur or Sublimed Sulfur.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step A,
Amines shown in the formula (Y) are generally 1 with the mol ratio of the vulcanizing agent: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 with
Carry out in the presence of the solvent.As the solvent, such as can enumerate C2-10Aliphatic nitrile (such as second
Nitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane is (such as just
Hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as methanol, ethanol, normal propyl alcohol, isopropanol,
N-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- bis-
Chlorobenzene), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as two
Methylformamide, dimethyl acetylamide and N-Methyl pyrrolidone) etc..These solvents can be used only
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, the additional step A is general
Carry out in the presence of a catalyst.As the catalyst, such as can enumerate prior art for this purpose
And the conventional catalyst for adopting, specifically such as iodine.As the consumption of the catalyst, can directly reference
The conventional amount used of prior art, is not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the additional step A's
Response time, 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 additional step A's
There is no particular limitation for reaction temperature, but generally 60 DEG C -300 DEG C, it is preferably 120 DEG C -240 DEG C, optimum
Select 150 DEG C -200 DEG C.
According to the present invention, in the preparation method of the shielding phenolic compounds, in additional step A knots
After beam, by conventionally known separation method (such as evaporation etc.) from additional step A obtain it is anti-
Answer and remove in mixture after the volatile material such as solvent that may be present, you can obtain additional step A's
Product, or follow-up reactions steps can also be directly used in (such as aforementioned without the separation
Additional step B).
An embodiment of the invention, it is described in the preparation method of the shielding phenolic compounds
Additional step B can be carried out (as independent step) after the first step terminates, it is also possible to
Carry out simultaneously with the first step, be not particularly limited.When the additional step B is described
When one step is carried out after terminating, the product of the first step is as previously mentioned from described first
Separate in the reactant mixture of step.Or, the product of the first step can also be without
The separation is crossed, and is directly used to carry out the extra step in the form of the reactant mixture of the first step
Rapid B.Or, the additional step B can also be carried out after the additional step A terminates.When
The additional step B after the additional step A terminates when carrying out, and the additional step A's is anti-
Answer product as described herein and 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 the additional step A
Reactant mixture form be used for carry out the additional step B.In addition, when the additional step B with
The first step is carried out simultaneously when, directly in the reaction system of the first step (such as described
The beginning of first step or during the first step is carried out) according to hereinafter provided consumption add
Aldehyde compound shown in the formula (Z).
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B,
As the aldehyde compound shown in the formula (Z), such as can enumerate C1-6Aliphatic aldehyde and benzaldehyde.
As the C1-6Aliphatic aldehyde, such as can enumerate C1-6Straight or branched saturated aliphatic aldehyde, concrete ratio
Such as acetaldehyde or formaldehyde, more preferably formaldehyde.As the formaldehyde, such as can use its aqueous solution, poly
Formaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B,
The mol ratio of the amines shown in the formula (Y) and the aldehyde compound shown in the formula (Z)
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 (makees
When carrying out for independent step) can carry out in the presence of the solvent.As the solvent, such as can be with
Enumerate C2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and
Isopropylbenzene), C6-10Alkane (such as normal hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol is (such as
Methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloro
Methane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10(such as acetone, butanone and methyl are different for ketone
Butyl ketone) or C3-10Amide (such as dimethylformamide, dimethyl acetylamide and N- methylpyrroles
Alkanone) etc..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, (make in the additional step B
When carrying out for independent step) in, catalyst can be added without, it is also possible to add catalyst.As institute
Catalyst is stated, such as can enumerate inorganic acid catalyst and organic acid catalyst.Urge as the mineral acid
Agent, such as can enumerate hydrochloric acid, sulphuric acid and phosphoric acid etc..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 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, the additional step B (is made
When carrying out for independent step) there is no particular limitation response time, but generally 0.1h-24h is excellent
Select 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step B (is made
When carrying out for independent step) reaction temperature there is no particular limitation, but generally 0 DEG C -250 DEG C,
It is preferred that 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, (make in the additional step B
When carrying out for independent step) terminate after, by conventionally known separation method (such as evaporation etc.)
Remove in the reactant mixture obtained from the additional step B volatile material such as solvent that may be present it
Afterwards, you can obtain the product of additional step B, or can also be directly used in without the separation
Follow-up reactions steps (than additional step A as the aforementioned).
Known in the art, aforementioned all of reactions steps are (including the first step, described attached
Plus step A and the additional step B) typically carry out under the protection of inert gas atmosphere.As described
Noble gases, such as can enumerate nitrogen and argon etc., be not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, as the first step
The product of product, the product of the additional step A or the additional step B,
Can be a kind of single shielding phenolic compounds (the shielding phenolic compounds such as shown in aforementioned formula (I)),
It can also be the mixture comprising various shielding phenolic compounds.These product are all desired by the present invention
, the difference of its existence form has no effect on the realization of effect of the present invention.Therefore, this specification context
In without distinction by these product be collectively termed as the present invention shielding phenolic compounds.In consideration of it, root
According to the present invention, do not exist and be further purified these product, or enter one from these product
Step isolates the absolute necessity of the shielding phenolic compounds of a certain ad hoc structure.Certainly, the purification or separation
It is sometimes preferred for the further lifting of Expected Results of the present invention, but for the present invention not
It is required.Even so, as the purification or separation method, such as can enumerate by column chromatography method
Or the method such as preparative hplc carries out purification or separation etc. to the product.
The present invention is further illustrated for below example, but and is not so limited the present invention.With
In lower embodiment, dropping point is measured using the methods of GB/T 3498, and cone penetration is surveyed using the methods of GB/T 269
, oxidation stability is measured using the methods of GB/T 13464, and Stencil oil-dividing adopts the methods of SH/T 0324
Measure, anticorrosive property is measured using the methods of GB/T 5018, tetra-ball machine test PB adopts SH/T 0202
Method is measured, and tetra-ball machine test PD is measured using the methods of SH/T 0202, and copper corrosion performance adopts GB/T
7326 methods are measured.
Embodiment 1
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.86 grams
(62mmol) formaldehyde, 28.15 grams of (153mmol) 4-aminodiphenylamines, 0.75 gram (7.5mmol)
Hydrochloric acid and 150mL isopropanols, rapid stirring, at 25 DEG C 24h is reacted.After question response terminates, decompression
Solvent and a small amount of water for generating are distilled off, and the shielding phenol for obtaining constituted above by column chromatography for separation is produced
Thing.
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 value of calculation C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Determine
Value：C 74.52, H 7.84, N 6.51, O 3.73, S 7.40.
The preparation of complex calcium lubricating grease：
Raw material components：500SN base oils：(100 DEG C of viscosity are 10mm to 1440kg2/s)；Hydroxide
Calcium 40.38kg；Acetic acid 31.8kg；Sad 54.58g；12- hydroxy stearic acid 45.48kg；Shielding phenolate
Compound 8kg；
First 720kg base oils and suspension containing 40.38kg calcium hydroxide are added in fat kettle processed, is stirred
Mixing.Acetic acid 31.8kg reaction 10min are added in room temperature；When temperature rises to 80 DEG C of addition 45.48kg
12- hydroxy stearic acid stirring reactions 30min；Add 54.58kg octanoic acid reaction 40min in system again.
It is warming up to 200 DEG C to keep adding 720kg base oils after refining temperature 20min, after cooling to 100 DEG C,
8kg shielding phenolic compounds are added, is stirred；By three-roller 3 times are ground into fat.Properties of product are such as
Shown in table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：12- hydroxyls are hard
Weight % of fat acid calcium 3.02；Calcium octoate weight 3.86%；Weight % of calcium acetate 2.62；Lubricating base oil 90
Weight %；Shielding weight % of phenolic compounds 0.5.
Embodiment 2
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 0.45 gram
(15mmol) formaldehyde, 10.14 grams of (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL first
Benzene, rapid stirring, at 90 DEG C 4h is reacted.After question response terminates, vacuum distillation removes solvent and generation
A small amount of water, 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), 5.23 (2H), 6.80-7.02
(10H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.2,117.1,121.8,126.2,
129.5,136.6,143.6,153.4；
C33H38N2OS value of calculation C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Determine
Value：C 77.71, H 7.52, N 5.53, O 3.10, S 6.23.
The preparation of complex calcium lubricating grease：
Raw material components：150BS lubricating base oils：(100 DEG C of viscosity are 30mm to 655kg2/s)；Hydroxide
Calcium 77.68kg；Acetic acid 88.94kg；P-phthalic acid 30.78g；12- hydroxy stearic acid 55.68kg；Screen
Cover phenolic compounds 3.51kg；
First 490kg lubricating base oils and suspension containing 77.68kg calcium hydroxide are added in fat kettle processed,
Stirring mixing.Acetic acid 88.94kg reaction 20min are added in room temperature；When temperature rises to 85 DEG C of additions
12- hydroxy stearic acid stirring reactions 90min of 55.68kg；30.78kg is added in system again to benzene two
Formic acid reacts 20min.It is warming up to 220 DEG C to keep adding 165kg lubricating base oils after refining temperature 5min,
After cooling to 130 DEG C, 3.51kg shielding phenolic compounds are added, stirred；3 are ground by three-roller
It is secondary into fat.Properties of product are as shown in table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：12- hydroxyls are hard
Weight % of fat acid calcium 6.85；P-phthalic acid calcium weight 4.60%；Weight % of calcium acetate 13.55；Lubrication
Weight % of base oil 74.6；Shielding weight % of phenolic compounds 0.4.
Embodiment 3
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.45 grams
(115mmol) formaldehyde, 18.49 grams of (69mmol) N- (1,3- dimethylbutyl)-N'- phenyl are to benzene two
Amine and 150mL benzene, rapid stirring, at 85 DEG C 3h is reacted.After question response terminates, vacuum distillation is removed
Solvent 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 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H),
1.67 (2H), 3.47 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H),
7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 17.9,22.4,29.6,34.6,45.2,52.7,
58.6,119.4,121.8,126.2,129.5,131.2,136.6,144.1,146.1,153.4；
C33H46N2OS value of calculation:C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measured value：
C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
The preparation of complex calcium lubricating grease：
Raw material components：PAO6 synthesized hydrocarbon fluid base oils：(100 DEG C of viscosity are 5.8mm to 640kg2/s)；
Calcium hydroxide 21.66kg；Acetic acid 14.5kg；Decanedioic acid 12.1g；Stearic acid 58.46kg；2.22kg screen
Cover phenolic compounds；
First 420kg lubricating base oils and suspension containing 21.66kg calcium hydroxide are added in fat kettle processed,
Stirring mixing.Acetic acid 14.5kg reaction 30min are added in room temperature；When temperature rises to 100 DEG C of additions
Stearic acid stirring reaction 40min of 58.46kg；Add 12.1kg decanedioic acid reaction 30min in system again.
It is warming up to 215 DEG C to keep adding 220kg lubricating base oils after refining temperature 8min, after cooling to 110 DEG C,
2.22kg shielding phenolic compounds are added, is stirred；By three-roller 2 times are ground into fat.Properties of product
As shown in table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Calcium stearate 8.60
Weight %；Weight % of decanedioic acid calcium 1.97；Weight % of calcium acetate 2.43；Weight % of lubricating base oil 86.7；
Shielding weight % of phenolic compounds 0.3.
Embodiment 4
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.59 grams
(53mmol) formaldehyde, 5.70 grams of (31mmol) 4-aminodiphenylamines and 150mL ethanol, it is fast
Speed stirring, after reacting 2.5h at 60 DEG C, is down to room temperature, adds 2.55 grams of (85mmol) formaldehyde, rises
Temperature to 85 DEG C are reacted 2.5h.After question response terminates, vacuum distillation removes solvent 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), 3.74 (1H), 4.12 (2H),
4.59 (1H), 4.83 (2H), 5.32 (1H), 6.97-7.11 (5H), 7.17 (2H), 7.24
(2H)；
13C NMR (75MHz, CDCl3)：δ 29.6,33.1,34.6,50.6,119.4,123.3,
126.2,126.7,127.9,136.6,140.5,142.9,153.4；
C26H34N2OS value of calculation C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Determine
Value：C 75.20, H 7.59, N 6.29, O 3.65, S 7.22.
The preparation of complex calcium lubricating grease：
Raw material components：The mixed lubrication base oil of 500SN and 150BS：(100 DEG C of viscosity are 830kg
13mm2/s)；Calcium hydroxide 57.34kg；Acetic acid 60.18kg；Caprylic acid 24.12g；Stearic acid 95.12kg；
Shielding phenolic compounds 2.08kg；
First 450kg lubricating base oils and suspension containing 57.34kg calcium hydroxide are added in fat kettle processed,
Stirring mixing.Acetic acid 60.18kg reaction 20min are added in room temperature；When temperature rises to 90 DEG C of additions
Stearic acid stirring reaction 60min of 95.12kg；Add the reaction of 24.12kg caprylic acids in system again
30min.It is warming up to 210 DEG C to keep adding 380kg lubricating base oils, cooling after refining temperature 10min
To after 110 DEG C, 2.08kg shielding phenolic compounds are added, stirred；By three-roller grind 2 times into
Fat.Properties of product are as shown in table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：Calcium stearate 9.75
Weight %；Weight % of caprylic acid calcium 2.63；Weight % of calcium acetate 7.62；Weight % of lubricating base oil 79.8；
Shielding weight % of phenolic compounds 0.2.
Embodiment 5
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.63 grams
(121mmol) formaldehyde, 19.93 grams of (94mmol) 4- amino -4'- ethyls diphenylamines and 150mL bis-
Toluene, rapid stirring after reacting 3h at 90 DEG C, is down to room temperature, adds 10.11 grams (316mmol)
Sulfur and 0.04 gram of (0.35mmol) iodine, are warming up to 150 DEG C of reaction 8h.After question response terminates, decompression
Solvent and a small amount of water for generating are distilled off, and the shielding phenol for obtaining constituted above by column chromatography for separation is produced
Thing.
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；
C29H36N2OS2Value of calculation C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Survey
Definite value：C 70.77, H 7.41, N 5.67, O 3.17, S 12.93.
The preparation of complex calcium lubricating grease：
Raw material components：500SN lubricating base oils：(100 DEG C of viscosity are 10mm to 1430kg2/s)；Hydrogen-oxygen
Change calcium 40.38kg；Acetic acid 31.8kg；Sad 54.58g；12- hydroxy stearic acid 45.48kg；Shielding phenol
Compound 1.58kg；
First 830kg lubricating base oils and suspension containing 40.38kg calcium hydroxide are added in fat kettle processed,
Stirring mixing.Acetic acid 31.8kg reaction 10min are added in room temperature；When temperature rises to 80 DEG C of additions
12- hydroxy stearic acid stirring reactions 40min of 45.48kg；Add 54.58kg octanoic acids anti-in system again
Answer 30min.It is warming up to 200 DEG C to keep adding 600kg lubricating base oils, drop after refining temperature 20min
Temperature adds 1.58kg shielding phenolic compounds to after 100 DEG C, stirs；Ground 3 times by three-roller
Into fat.Properties of product are as shown in table 1.
In the grease that the present embodiment is obtained, on the basis of grease weight, consist of：12- hydroxyls are hard
Weight % of fat acid calcium 3.02；Calcium octoate weight 3.86%；Weight % of calcium acetate 2.62；Lubricating base oil 90.4
Weight %；Shielding weight % of phenolic compounds 0.1.
Comparative example 1
Method according to embodiment 4 prepares complex calcium lubricating grease, except for the difference that, complex calcium lubricating grease
Preparation process in be added without shield phenolic compounds.Properties of product are as shown in table 1.
Comparative example 2
Method according to embodiment 4 prepares complex calcium lubricating grease, except for the difference that, by 2,6- di-t-butyls
Shielding phenolic compounds in p-cresol (its structure sees below formula) alternate embodiment 4, obtain grease group
The comparative example 2 of compound.Properties of product are as shown in table 1.
Comparative example 3
Method according to embodiment 4 prepares complex calcium lubricating grease, except for the difference that, by N- phenyl-α-naphthalene
Shielding phenolic compounds in amine alternate embodiment 4, obtain the comparative example 3 of lubricant composition.Product
Can be as shown in table 1.
Comparative example 4
Method according to embodiment 4 prepares complex calcium lubricating grease, is following formula by structure except for the difference that
Shielding phenolic compounds in shielding phenolic compounds alternate embodiment 4, obtain the comparative example of lubricant composition
4.Properties of product are as shown in table 1.
The preparation of the shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.61 grams
(87mmol) formaldehyde, 14.37 grams of (85mmol) diphenylamines and 150mL methanol, rapid stirring,
2h is reacted at 60 DEG C.After question response terminates, vacuum distillation removes solvent 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 value of calculation C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Determine
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 complex calcium lubricating grease, is following formula by structure except for the difference that
Shielding phenolic compounds in shielding phenolic compounds alternate embodiment 4, obtain the comparative example of lubricant composition
5.Properties of product are as shown in table 1.
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams
(63mmol) formaldehyde, 17.42 grams of (65mmol) N- (1,3- dimethylbutyl)-N'- phenyl are to benzene two
Amine and 150mL methanol, rapid stirring, at 70 DEG C 4h is reacted.After question response terminates, vacuum distillation
Solvent and a small amount of water for generating are removed, and the shielding phenol for obtaining constituted above by column chromatography for separation is produced
Thing.
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 value of calculation C 81.43, H 9.53, N 5.76, O 3.29；Measured value：C 81.38,
H 9.51, N 5.79, O 3.31.
Comparative example 6
Method according to embodiment 4 prepares complex calcium lubricating grease, is following formula by structure except for the difference that
Shielding phenolic compounds in shielding phenolic compounds alternate embodiment 4, obtain the comparative example of lubricant composition
6.Properties of product are as shown in table 1.
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, in the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, 9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyis) phenol are added,
1.11 grams of (37mmol) formaldehyde, 11.71 grams of (45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and
150mL benzene, rapid stirring, at 80 DEG C 4h 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 product ability characterize data 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 value of calculation C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Determine
Value：C 78.27, H 7.96, N 4.98, O 2.92, S 5.83
The assessment of performance of the grease of table 1
As it can be seen from table 1 the complex calcium lubricating grease of the present invention has excellent high temperature antioxidant, prevents
Rust property, heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life,
The performance such as anticorrosive property and resistance to saltfog.
Claims (16)
1. a kind of complex calcium lubricating grease, on the basis of grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the composite calcium-base thickening agent and major amount of lubrication base of 5%-35%
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, and is each independently selected from hydrogen, C1-300Directly
Chain or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
It is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III), 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, each independent
Ground is selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight or branched
Alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other, each
It is independently groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain
Or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched alkane
Base and C3-10Straight or branched miscellaneous alkyl；Each group R2It is same to each other or different to each other, is each independently selected from
Hydrogen, C1-20Group and the group shown in logical formula V shown in straight or branched alkyl, logical formula (IV)
(preferably it is each independently selected from hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV))；
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Straight or branched alkyl is (excellent
Choosing is each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group RcIt is same to each other or different to each other,
It is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl epoxide is (preferably
It is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, it is more excellent
Choosing is in cyclic groupThe para-position of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；
Z is 0 to 3 integer (preferably 0 or 1)；N is 1 to 8 integer (preferably 1 or 2)；N' is 0
To 7 integer (preferably 0,1 or 2), on condition that n'+n≤8 (preferred n'+n=1 or n'+n=2)；Respectively
Group RdIt is same to each other or different to each other, is each independently selected from hydrogen and the group shown in logical formula V (preferably
Hydrogen)；Each 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), wherein two adjacent cyclic groupsEach other optionally by additional S atom and bridge
Connect the N atoms of the two rings and form phenothiazine ring, and/or, two adjacent cyclic groups
Each other optionally by additional group(wherein group R " it is selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10Directly
Chain 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, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
It is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III) (preferably each solely
On the spot selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' is same to each other or different to each other, each independent
Ground is selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight or branched
Alkyl)；Group L is groupWherein group R " 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, C1-10Straight chain
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 selected from inside straight or branched alkyl molecular structure
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- be selected from
(R' is H or C for-O- ,-S- and-NR'-1-4Straight or branched alkyl) one of substituting group directly replace
Generation and obtain group and straight or branched alkyl molecular structure inside one or more (such as 1 to 3
It is individual, 1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining,
The wherein shielding phenolic compounds at least one group R in its whole molecular structuredIt is hydrogen.
2. according to the grease described in claim 1, it is characterised in that described shielding phenolate is closed
Mixture of the thing selected from following particular compound or its arbitrary proportion：
3. according to the grease described in claim 1, it is characterised in that the shielding phenolic compounds
Preparation method include making the phenolic compounds and the amines shown in formula (Y) shown in logical formula (X)
The first step reacted in the presence of the aldehyde compound (preferred formaldehyde) shown in formula (Z),
Optionally also include making the product of the first step react with vulcanizing agent (preferred sulfur) and/or and formula
(Z) additional step of aldehyde compound (preferred formaldehyde) reaction shown in,
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from hydrogen ,-SH
And C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is polyolefin-based for 300-3000's), on condition that at least one group R0It is-SH；Each group R' that
This is identical or different, is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably independently of one another
Selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Directly
Chain or branched alkyl (are preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group Rc
It is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain is propped up
Alkyl group epoxide (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight chain is propped up
Alkyl group epoxide, is more preferably in cyclic groupThe para-position 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)；Each cyclic groupIt is same to each other or different to each other, is each independently selected from phenyl ring
With naphthalene nucleus (preferred phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl)
And C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight chain
Or branched heteroalkyl groups,
Wherein, the straight or branched miscellaneous alkyl is selected from inside straight or branched alkyl molecular structure
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- be selected from
(R' is H or C for-O- ,-S- and-NR'-1-4Straight or branched alkyl) one of substituting group directly replace
Generation and obtain group and straight or branched alkyl molecular structure inside one or more (such as 1 to 3
It is individual, 1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining.
4. according to the grease described in claim 3, it is characterised in that wherein in the first step
In, the phenolic compounds shown in the logical formula (X) rub with the amines shown in the formula (Y)
You are than being 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, the phenol shown in the logical formula (X)
Compound is 1 with the mol ratio of the aldehyde compound shown in the formula (Z):0.1-10, preferably 1:0.5-5.0,
More preferably 1:0.8-2.0, the amines and institute in the additional step, shown in the formula (Y)
The mol ratio for stating vulcanizing agent is 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0, the formula (Y)
Shown amines are 1 with the mol ratio of the aldehyde compound shown in the formula (Z):0.1-10, preferably
1:0.5-5.0, more preferably 1:0.8-2.0.
5. according to the grease described in claim 1, it is characterised in that the shielding phenolic compounds are accounted for
The 0.05%-5% of the complex calcium lubricating grease composition total weight.
6. according to the grease described in claim 1, it is characterised in that the composite calcium-base thickening agent
Generated with calcium hydroxide reaction by acid, the acid is the mixed of polymer acid, the acid of middle molecule and low molecular acid
Acid is closed, the polymer acid is C12-C25 fatty acids and/or hydroxy fatty acid；The middle molecule acid is
C6-C10 carboxylic acids；The low molecular acid is C2-C5 carboxylic acids.
7. according to the grease described in claim 6, it is characterised in that the polymer acid is Laurel
One or more in acid, Palmic acid, stearic acid and 12- hydroxy stearic acids；The middle molecule acid is pungent
One or more in acid, benzoic acid, p-phthalic acid, Azelaic Acid and decanedioic acid；The low molecular acid
For acetic acid.
8. according to the grease described in claim 6, it is characterised in that the polymer acid divides with
The mol ratio of sub- acid is 0.37-3.4：1；The molal quantity of the low molecular acid and polymer acid, the acid of middle molecule
The ratio of molal quantity sum is 0.9-4：1.
9. according to the grease described in claim 1, it is characterised in that the lubricating base oil is ore deposit
One or more in thing oil, vegetable oil and artificial oil, its 100 DEG C of kinematic viscositys are 5-60mm2/s。
10. the preparation method of the complex calcium lubricating grease described in claim 1, including：By composite calcium-base
Thickening agent and lubricating base oil mix homogeneously, in 180-230 DEG C of constant temperature refining, are cooled to 100-130 DEG C,
The shielding phenolic compounds are added, fat is ground to form.
The preparation method of the complex calcium lubricating grease described in 11. claim 1, including：By partial lubrication
Saponification is carried out at normal temperatures with low molecular acid after base oil and calcium hydroxide mixing, treats that temperature rises to
When 80-100 DEG C, polymer acid is added to carry out saponification, after reaction completely, molecule acid in addition is carried out
Saponification, is warming up to 200-220 DEG C and is refined after reaction completely, is subsequently adding remaining lubrication base
Plinth oil cooling adds the shielding phenolic compounds to 100-130 DEG C, grinds to form fat.
12. in accordance with the method for claim 10, it is characterised in that the calcium hydroxide and low molecule
The reaction temperature of acid is 15-50 DEG C, and the time for carrying out saponification with low molecular acid is 1-60 minutes, with
Middle molecule acid carry out saponification time be 5-60 minutes, with polymer acid carry out saponification when
Between be 10-120 minutes.
13. in accordance with the method for claim 10, it is characterised in that the partial lubrication base oil with
The weight ratio of remaining lubricating base oil is 50-75：25-50.
14. in accordance with the method for claim 10, it is characterised in that the polymer acid and middle molecule
The mol ratio of acid is 0.37-3.4：1；The molal quantity of the low molecular acid rubs with polymer acid, middle molecule acid
The ratio of your number sum is 0.9-4：1.
15. in accordance with the method for claim 10, it is characterised in that polymer acid, middle molecule acid and
The total amount of low molecular acid and the mol ratio of calcium hydroxide are the equivalent ratio for completing saponification.
16. in accordance with the method for claim 10, it is characterised in that the refining time is 5-20
Minute.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254346A (en) * | 2017-06-14 | 2017-10-17 | 太原理工大学 | A kind of calcium zirconyl phosphate base grease and preparation method thereof |
| CN107523383A (en) * | 2017-08-01 | 2017-12-29 | 太原理工大学 | A kind of environment-friendly type stratiform potassium phosphate calcium calcium-base grease and preparation method thereof |
| CN109679722A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Complex calcium lubricating grease and preparation method thereof |
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| CA1219584A (en) * | 1983-02-10 | 1987-03-24 | John D. Spivack | N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers |
| US4946610A (en) * | 1989-08-03 | 1990-08-07 | Ethyl Petroleum Additives, Inc. | Sulfur-bridged phenolic antioxidants |
| CN1534084A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Preparation method of antioxidation antifriction lubricating oil additive |
| 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 |
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| CA1219584A (en) * | 1983-02-10 | 1987-03-24 | John D. Spivack | N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers |
| US4946610A (en) * | 1989-08-03 | 1990-08-07 | Ethyl Petroleum Additives, Inc. | Sulfur-bridged phenolic antioxidants |
| CN1534084A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Preparation method of antioxidation antifriction lubricating oil additive |
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|---|---|---|---|---|
| CN107254346A (en) * | 2017-06-14 | 2017-10-17 | 太原理工大学 | A kind of calcium zirconyl phosphate base grease and preparation method thereof |
| CN107254346B (en) * | 2017-06-14 | 2020-04-21 | 太原理工大学 | Calcium zirconium phosphate-based lubricating grease and preparation method thereof |
| CN107523383A (en) * | 2017-08-01 | 2017-12-29 | 太原理工大学 | A kind of environment-friendly type stratiform potassium phosphate calcium calcium-base grease and preparation method thereof |
| CN107523383B (en) * | 2017-08-01 | 2020-01-31 | 太原理工大学 | Environment-friendly layered calcium potassium phosphate grease and preparation method thereof |
| CN109679722A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Complex calcium lubricating grease and preparation method thereof |
| CN109679722B (en) * | 2017-10-18 | 2022-05-03 | 中国石油化工股份有限公司 | Composite calcium-based lubricating grease and preparation method thereof |
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| CN106590886B (en) | 2019-08-16 |
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