CN106590821A - Complex aluminum-based lubricating grease and preparation method thereof - Google Patents
Complex aluminum-based lubricating grease and preparation method thereof Download PDFInfo
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- CN106590821A CN106590821A CN201510664814.XA CN201510664814A CN106590821A CN 106590821 A CN106590821 A CN 106590821A CN 201510664814 A CN201510664814 A CN 201510664814A CN 106590821 A CN106590821 A CN 106590821A
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Abstract
The invention provides complex aluminum-based lubricating grease and a preparation method thereof. The lubricating grease is prepared from components in terms of the total weight of lubricating grease as follows: 0.01%-10% of a shielding phenol compound, 5%-35% of a complex lithium-calcium-based thickening agent and a major amount of lubricating base oil; the structure of the shielding phenol compound is shown in the specification. The complex aluminum-based lubricating grease has high dropping point, good mechanical stability, excellent thermal stability, colloid stability, high-temperature oxidation resistance, antirust performance, water spraying resistance and extreme pressure property, can be qualified for lubrication of various motors, generators, air blowers, transportation industry, iron and steel enterprises and other industrial equipment and is particularly applicable to lubrication of ship machinery under higher temperature and humid conditions.
Description
Technical field
The present invention relates to a kind of grease, more particularly to a kind of composite aluminum base grease.
Background technology
The research of composite aluminum base grease starts from the 1950's, but is just subject to weight until the seventies
Depending on, it is mainly used in the concentration of steel plant for fat system, yield is only second to compound lithium base in complex-soap base grease
Grease occupies second.Composite aluminum base grease is a kind of high temperature multi-effect grease.
CN 102021067A are prepared for a kind of suitable for barium aluminum lubricating grease for ships；CN
102021068A is prepared for a kind of suitable for sodium aluminate soap grease for ship；CN 1900244A are to compound
Introduce in aluminium-base grease sulfoacid calcium preparation composite aluminum base grease in the case of not doping,
Improve mechanical stability and high temperature colloid stability.
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
Content of the present invention including the following aspects：
1. a kind of composite aluminum base grease, on the basis of grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the composite aluminum 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, selected from following particular compound
Or the mixture of its arbitrary proportion：
3. the preparation method of the shielding phenolic compounds described in any preceding aspect, including making logical formula (X)
Amines shown in shown phenolic compounds and formula (Y) are in the aldehyde compound shown in formula (Z)
The first step reacted in the presence of (preferred formaldehyde), optionally also includes making the first step
Product is reacted and/or (preferred with the aldehyde compound shown in formula (Z) with vulcanizing agent (preferred sulfur)
Formaldehyde) reaction additional 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 composite aluminum base grease described in any preceding aspect, wherein the shielding phenolic compounds account for institute
The 0.01%-10% of composite aluminum base grease composition total weight, preferred 0.05%-5% are stated, more preferably
0.1%-0.5%.
The composite aluminum base thickening agent of the present invention can be generated by acid with silicon source reaction, the acid preferably high score
Sub- acid and the mixed acid of low molecular acid.The polymer acid is C12-C25 fatty acids and/or hydroxy aliphatic
Acid, can be one or more in lauric acid, Palmic acid, stearic acid and 12- hydroxy stearic acids, excellent
Select stearic acid and/or 12- hydroxy stearic acids；The low molecular acid can be C4-C11 carboxylic acids, preferred benzene
One or more in formic acid, p-phthalic acid, Azelaic Acid and decanedioic acid.The polymer acid with low point
The mol ratio of sub- acid is preferably 1：0.1-5, more preferably 1：0.3-2.
In the present invention, source of aluminium is the material that saponification forms aluminium soap can occur with acid, preferably different
One or more in Aluminum tripropoxide, aluminum isopropylate. trimer and aluminum sulfate.
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 dithio two
Alkyl phosphoric acid zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formate, triphenyl
Thiophosphate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, politef, D2EHDTPA
Molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite,
At least one in Calcium Carbonate and Zinc Oxide；Antirust agent accounts for the 0.01-4.5% of grease gross weight, preferably
0.1-2%, can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, aphthenic acids
At least one in zinc and alkenyl succinic acid.
In the present invention, the content of each component is calculated according to inventory in grease composition.Wherein,
Amount=100% of composite aluminum base thickening agent × (weight of the weight of polymer acid aluminum+low molecular acid aluminum)/profit
Consistent lubricant gross weight.
The invention provides the preparation method of aforementioned composite aluminum base grease, including：Composite aluminum base is thickened
Agent and partial lubrication base oil mix homogeneously, in 200-220 DEG C of constant temperature refining, add remaining lubrication base
Plinth oil, is cooled to 100-130 DEG C, adds foregoing shielding phenolic compounds, grinds to form fat.
The preparation method of the preferred aforementioned composite aluminum base grease of the present invention, including：
Partial lubrication base oil, polymer acid, silicon source are carried out in a heated condition saponification, then
Add low molecular acid to carry out saponification, refined at 200-220 DEG C, add remaining lubrication base
Plinth oil cooling adds foregoing shielding phenolic compounds to 100-130 DEG C, grinds to form fat.
Wherein, the temperature of the saponification is preferably 80-100 DEG C, and the time of each saponification is preferred
For 0.5-1.5 hours.The time of the refining is preferably 5-25 minutes.
By weight, the ratio between the partial lubrication base oil and remaining lubricating base oil is
50-75：25-50.
The polymer acid is preferably 1 with the mol ratio of low molecular acid:0.1-5, more preferably 1:0.3-2.It is high
Preferably there is the equivalent ratio of saponification with the mol ratio of silicon source in the total amount of molecule acid and low molecular acid,
Wherein the amount of silicon source can also excess 1-10 weight %.
It should be noted that when source of aluminium is aluminum isopropylate. rather than aluminum isopropylate. trimer or isopropanol
When containing aluminum isopropylate. in aluminum trimer, refine in forward reaction system generally also after saponification and add
Appropriate water, so that saponification is fully carried out.
The composite aluminum base grease that the present invention is provided has high dropping point, good mechanical stability, excellent
Heat stability, colloid stability, high temperature antioxidant, rustless property, anti-water drenching energy and extreme pressure property,
Various motors, electromotor, aerator, transportation, iron and steel enterprise can be competent in and other are various
The lubrication of industrial equipment, is particularly well-suited to the lubrication of ships plant equipment under higher temperature wet condition.
Specific embodiment
In the composite aluminum base grease of the present invention, the shielding phenolic compounds being related to shown in a kind of 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, 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, water drenches number of dropouts and adopts the methods of SH/T 0109
Measure, copper corrosion performance is measured using the methods of GB/T 7326.
Embodiment 1
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, 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 composite aluminum base grease：
Raw material components：(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 1470g2/s)；12- hydroxyls
Stearic acid 81.88g；Benzoic acid 9.98g；Aluminum isopropylate. trimer 36.7g；Water 5g；1.6g shields phenol
Compound.
By 735 grams of lubricating base oils, 81.88 grams of 12- hydroxy stearic acids and 36.7 grams of aluminum isopropylate. trimerizations
Body is added in fat kettle processed, and agitating heating is warming up to 80 DEG C, carries out saponification 0.5h；By 9.98 grams of benzene
Formic acid is added in fat kettle processed and carries out saponification 0.5h；5 grams of water are added, 5min is kept；Continue to stir
210 DEG C are warming up to, 5min is kept；735 grams of lubricating base oils are added, treat that temperature is cooled to 110 DEG C,
1.6 grams of shielding phenolic compounds are added, is stirred, 3 times are ground into fat by three-roller.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：12- hydroxyls are hard
Weight % of fat acid aluminum 7.3；Weight % of aluminum benzoate 0.7；Weight % of lubricating base oil 91.9；Shielding phenolate
Weight % of compound 0.1.
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 composite aluminum base grease：
Raw material components：(100 DEG C of viscosity are 30mm to 150BS lubricating base oil 954g2/s)；12- hydroxyls
Stearic acid 76.82g；P-phthalic acid 84.94g；Aluminum isopropylate. trimer 79.12g；Water 8g；6g
Shielding phenolic compounds.
By 554 grams of lubricating base oils, 76.82 grams of 12- hydroxy stearic acids and 79.12 grams of aluminum isopropylate. trimerizations
Body is added in fat kettle processed, and agitating heating is warming up to 100 DEG C, carries out saponification 0.5h；By 84.94 grams
P-phthalic acid is added in fat kettle processed and carries out saponification 0.5h；8 grams of water are added, 20min is kept；After
Continuous stirring is warming up to 220 DEG C, keeps 8min；400 grams of lubricating base oils are added to treat that temperature is cooled to 100 DEG C,
Add 6g shielding phenolic compounds.Stir, 3 times are ground into fat by three-roller.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 aluminum 9.48；Weight % of p-phthalic acid aluminum 10.52；Weight % of lubricating base oil 79.5；
Shielding weight % of phenolic compounds 0.5.
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；Determine
Value：C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
The preparation of composite aluminum base grease：
Raw material components：(100 DEG C of viscosity are 5.8mm to PAO6 synthesized hydrocarbon fluid base oil 898g2/s)；
Stearic acid 130.38g；P-phthalic acid 76.14g；Aluminum isopropylate. trimer 94.02g；Water 6g；2.4g
Shielding phenolic compounds.
673 grams of lubricating base oils, 130.38 grams of stearic acid and 94.02 grams of aluminum isopropylate. trimers are added
In fat kettle processed, agitating heating is warming up to 85 DEG C, carries out saponification 0.5h；By 76.14 grams of terephthaldehydes
Sour addition in fat kettle processed carries out saponification 0.5h；6 grams of water are added, 2min is kept；Continue to stir
200 DEG C are warming up to, 10min is kept；225 grams of lubricating base oils are added to treat that temperature is cooled to 105 DEG C,
9.6g shielding phenolic compounds are added, is stirred, 2 times are ground into fat by three-roller.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：Aluminium stearate
15.83 weight %；Weight % of p-phthalic acid aluminum 9.17；Weight % of lubricating base oil 74.8；Shielding phenol
Weight % of compound 0.2.
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 composite aluminum base grease：
Raw material components：(100 DEG C of viscosity are the mixed lubrication base oil 1355g of 150BS and 500SN
13mm2/s)；Stearic acid 136.96g；Benzoic acid 29.36g；Aluminum isopropylate. trimer 74.5g；Water 10g；
4.8g shields phenolic compounds.
900 grams of lubricating base oils, 136.96 grams of stearic acid and 74.5 grams of aluminum isopropylate. trimers are added into system
In fat kettle, agitating heating is warming up to 95 DEG C, carries out saponification 0.5h；29.36 grams of benzoic acid are added
Saponification 0.5h is carried out in fat kettle processed；10 grams of water are added, 10min is kept；Continue stirring to be warming up to
205 DEG C, keep 15min；Add 455 grams of lubricating base oils to treat that temperature is cooled to 120 DEG C, add 4.8g
Shielding phenolic compounds, stir, and 2 times are ground into fat by three-roller.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：Aluminium stearate
12.35 weight %；Weight % of aluminum benzoate 2.65；Weight % of lubricating base oil 84.7；Shielding phenolate is closed
Weight % of thing 0.3.
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 composite aluminum base grease：
Raw material components：(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 1075g2/s)；12- hydroxyls
Base stearic acid 81.88g；Benzoic acid 9.98g；Aluminum isopropylate. trimer 36.7g；Water 5g；4.8g shielding
Phenolic compounds.
By 600 grams of lubricating base oils, 81.88 grams of 12- hydroxy stearic acids and 36.7 grams of aluminum isopropylate. trimerizations
Body is added in fat kettle processed, and agitating heating is warming up to 80 DEG C, carries out saponification 0.5h；By 9.98 grams of benzene
Formic acid is added in fat kettle processed and carries out saponification 0.5h；5 grams of water are added, 5min is kept；Continue to stir
210 DEG C are warming up to, 5min is kept；475 grams of lubricating base oils are added to treat that temperature is cooled to 110 DEG C, plus
Enter 4.8 grams of shielding phenolic compounds, stir, 3 times are ground into fat by three-roller.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 aluminum 9.7；Weight % of aluminum benzoate 0.9；Weight % of lubricating base oil 89.6；Shielding phenolate
Weight % of compound 0.4.
Comparative example 1
Method according to embodiment 4 prepares composite aluminum base grease, except for the difference that, composite aluminum base 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 composite aluminum base grease, except for the difference that, by 2,6- di-t-butyls
Shielding phenolic compounds in p-cresol (structure sees below formula) alternate embodiment 4, obtain grease composition
The comparative example 2 of thing.Properties of product are as shown in table 1.
Comparative example 3
Method according to embodiment 4 prepares composite aluminum base grease, except for the difference that, by N- phenyl-α-naphthalene
Shielding phenolic compounds in amine (structure sees below formula) alternate embodiment 4, obtain the right of lubricant composition
Ratio 3.Properties of product are as shown in table 1.
Comparative example 4
Method according to embodiment 4 prepares composite aluminum base 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 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 composite aluminum base 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 composite aluminum base 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 characterize data of the product is as follows：
1H NMR (300MHz, CDCl3)：δ 1.40 (18H), 1.99 (1H), 2.61-2.80
(6H), 4.63 (2H), 5.32 (1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 28.7,31.1,34.3,35.7,54.1,117.1,
119.4,123.3,124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS 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
From the results shown in Table 1, composite aluminum base grease of the invention has excellent high temperature antioxygen
Property, rust-preventing characteristic, heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, lubrication
The performances such as life-span, anticorrosive property and resistance to saltfog.
Claims (17)
1. a kind of composite aluminum base grease, on the basis of grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the composite aluminum 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 composite aluminum base grease composition total weight.
6. according to the grease described in claim 1, it is characterised in that the composite aluminum base thickening agent
Generated with silicon source reaction by acid.
7. according to the grease described in claim 6, it is characterised in that the acid for polymer acid and
The mixed acid of low molecular acid, the polymer acid is C12-C25 fatty acids and/or hydroxy fatty acid, institute
It is C4-C11 carboxylic acids to state low molecular acid, and the polymer acid is 1 with the mol ratio of low molecular acid：0.1-5.
8. according to the grease described in claim 7, 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 low molecular acid is benzene
One or more in formic acid, p-phthalic acid, Azelaic Acid and decanedioic acid.
9. according to the grease described in claim 6, it is characterised in that source of aluminium is can be with acid
There is the material that saponification forms aluminium soap.
10. according to the grease described in claim 6, it is characterised in that source of aluminium be aluminum isopropylate.,
One or more in aluminum isopropylate. trimer and aluminum sulfate.
11. 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。
The preparation method of the composite aluminum base grease described in 12. claim 1, including：By composite aluminum base
Thickening agent and partial lubrication base oil mix homogeneously, in 200-220 DEG C of constant temperature refining, add remaining profit
Sliding base oil, is cooled to 100-130 DEG C, adds the shielding phenolic compounds, grinds to form fat.
The preparation method of the composite aluminum base grease described in 13. claim 1, including：By partial lubrication
Base oil, polymer acid, silicon source carry out in a heated condition saponification, are subsequently adding low molecular acid and enter
Row saponification, is refined at 200-220 DEG C, adds remaining lubricating base oil to be cooled to
100-130 DEG C, the shielding phenolic compounds are added, grind to form fat.
14. in accordance with the method for claim 13, it is characterised in that described saponification each time is anti-
The temperature answered is 80-100 DEG C, and the time is 0.5-1.5 hours.15. according to the side described in claim 13
Method, it is characterised in that the time of the refining is 5-25 minutes.
15. in accordance with the method for claim 13, it is characterised in that the partial lubrication base oil
It is 50-75 with the ratio between remaining lubricating base oil：25-50.
16. in accordance with the method for claim 13, it is characterised in that the polymer acid with low point
The mol ratio of sub- acid is 1：0.1-5.
17. in accordance with the method for claim 13, it is characterised in that the polymer acid and low point
The sub- total amount of acid and the equivalent ratio that the mol ratio of silicon source is generation saponification.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679731A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Composite aluminum base grease and preparation method thereof |
| CN109943383A (en) * | 2019-02-26 | 2019-06-28 | 天津市金海利油脂有限公司 | A kind of Hmp grease thickening soap powder and its production technology |
| CN111117728A (en) * | 2019-12-12 | 2020-05-08 | 郴州市耐普电源有限公司 | High-temperature-resistant grease for casting mold opening of cast plate mold and preparation process |
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| CN109679731A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Composite aluminum base grease and preparation method thereof |
| CN109943383A (en) * | 2019-02-26 | 2019-06-28 | 天津市金海利油脂有限公司 | A kind of Hmp grease thickening soap powder and its production technology |
| CN111117728A (en) * | 2019-12-12 | 2020-05-08 | 郴州市耐普电源有限公司 | High-temperature-resistant grease for casting mold opening of cast plate mold and preparation process |
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| CN106590821B (en) | 2019-08-16 |
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