CN106590826B - Steam turbine lubricating oil composition and its manufacturing method - Google Patents

Steam turbine lubricating oil composition and its manufacturing method Download PDF

Info

Publication number
CN106590826B
CN106590826B CN201510674625.0A CN201510674625A CN106590826B CN 106590826 B CN106590826 B CN 106590826B CN 201510674625 A CN201510674625 A CN 201510674625A CN 106590826 B CN106590826 B CN 106590826B
Authority
CN
China
Prior art keywords
group
linear
hydrogen
branched alkyl
steam turbine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510674625.0A
Other languages
Chinese (zh)
Other versions
CN106590826A (en
Inventor
苏朔
龙军
段庆华
张辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing General Fine Chemical Technology Development Co ltd
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petrochemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201510674625.0A priority Critical patent/CN106590826B/en
Publication of CN106590826A publication Critical patent/CN106590826A/en
Application granted granted Critical
Publication of CN106590826B publication Critical patent/CN106590826B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Lubricants (AREA)

Abstract

The present invention relates to a kind of steam turbine lubricating oil compositions, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, antirust agent, anti emulsifier and major amount of lube base oil；The structure of the shielding phenolic compounds is shown in formula (I):

Description

Steam turbine lubricating oil composition and its manufacturing method
Technical field
The present invention relates to a kind of steam turbine lubricating oil compositions.Specifically, the present invention relates to one kind to have excellent high temperature The steam turbine lubricating oil composition of oxidation stability.
Background technique
Steam turbine is one of power generating industry main equipment, and power drive has the forms such as steam, combustion gas and waterpower.Vapour used Turbine lubricating oil is also known as turbine oil, generally includes steam turbine lubricating oil, gas turbine lubricating oil and waterpower turbo-engine lube Deng being mainly used for the lubrication of sliding bearing, reduction gearing, governor and hydraulic system etc. of steam turbine and the unit that is connected.
Steam turbine, combustion gas steam turbine and the waterpower steam turbine being widely used at present require that turbo-engine lube has Higher bearing capacity and longer service life.Steam turbine is that a kind of thermal energy by steam is rotating mechanical energy High-speed rotary thermal power is mechanical, its lubricant housings is mainly gearbox and rotor bearing, because its rotor axle envelope may have Vapour is altered, therefore a possibility that lubricating system water inlet, is larger, equipment revolving speed is high in addition, load is big, the cycle of operation is long, therefore to lubrication Oil rust-preventing characteristic, resistance to emulsion and it is antioxidative require it is all very high, also require lubricating oil to be formed in the key position of system heavy The tendency of product object is minimum.From conventional steam steam turbine as unlike combustion heating generates steam acting, gas turbine utilizes combustion It burns the combustion gas generated directly to do work, temperature reaches as high as 260 DEG C at bearing.Work of the combustion gas turbo-engine lube by bearing hot surface With and used under speed-regulating system high pressure, should have excellent oxidation stability and thermal stability, good rustless property and resist Emulsifiability.For gear-driven steam turbine, the extreme-pressure anti-wear bearing capacity that should have also had is set with meeting system middle gear Standby lubricating requirement.Turbo-engine lube used in steam-gas Combined circulatory system should meet steam turbine lubrication and want It asks, also to meet the lubrication requirement of combustion gas steam turbine, need fabulous high temperature oxidation resisting and corrosion resistance.
In recent years, it having been significantly increased with the output power of steam turbine with the ratio between oil mass, i.e., recycle ratio significantly increases, Cause steam turbine working condition harsher, operating temperature is sharply increased, and necessarily cause oil ageing degradation speed to be accelerated, this It requires that turbo-engine lube has the splendid performance of stable operation under the high temperature conditions, does not need only to have excellent extreme pressure and hold Loading capability, inoxidizability outstanding, while also there is good anti-foaming property and resistance to emulsion.
Seek more efficiently antioxidant additive and develop the turbo-engine lube of novel high-performance, is always this field skill The target that art personnel make great efforts.
United States Patent (USP) US 5304314A discloses a kind of phenolate conjunction for being suitable as sulfur-bearing and arylamine that antioxidant uses Object.United States Patent (USP) US 2006/0189824A1 discloses a kind of shielding phenol containing secondary aromatic amine for being suitable as antioxidant and using Compound.
But the compound of these prior arts in turbo-engine lube in use, the high-temperature oxidation resistance of oil product, Extreme pressure bearing capacity and abrasion resistance still remain room for improvement.In addition, other than the adverse effect of deposit, engine Corrosion also can serious curtailment engine service life, and the corrosion of some key positions largely also influences engine Performance of operating condition.The prior art is also far from enough to the concern of rustless property.
Therefore, a kind of steam turbine lubricating oil composition is still required in the prior art, is not only able to meet current higher rule The requirement increasingly harsh to high-temperature oxidation resistance of lattice product, and also show excellent extreme pressure property, detergent-dispersant performance energy, Abrasion resistance and rustless property.
Summary of the invention
The present invention relates to the contents of following aspect.
1. a kind of steam turbine lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, antirust Agent, anti emulsifier and major amount of lube base oil；
The structure of the shielding phenolic compounds are as follows:
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II) Group shown in group and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；Each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Straight chain Or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V) Group (is preferably each independently selected from hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV))；Each group RbEach other It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-10Straight chain Or branched alkyl)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Directly Chain or branched alkyl oxygroup (are preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen Base is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3 Integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n is 1 to 8；The integer (preferably 0,1 or 2) that n' is 0 to 7, on condition that n'+ N≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same or different to each other, is each independently selected from hydrogen and logical formula (V) institute The group (preferably hydrogen) shown；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring), wherein two adjacent cyclic groupsOptionally pass through additional S atom each other and bridges the two The N atom of ring and form phenthazine ring, and/or, two adjacent cyclic groupsOptionally pass through additional base each other Group(wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or Branched heteroalkyl groups are preferably selected from hydrogen and C1-10Linear or branched alkyl group) and bridge the N atom of the two rings and form 9,10- bis- Hydrogen acridine ring,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II) Group shown in group and logical formula (III) (is preferably each independently selected from hydrogen and C1-300Linear or branched alkyl group)；Each group R' that This is identical or different, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Directly Chain or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain Or branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Straight chain or branch Chain miscellaneous alkyl；A is 0 or 1, and two group R and a group-(S)a- L- occupies three positions of the residue on phenyl ring respectively,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- O- ,-S- and-NR'- are selected from (wherein in-NR'- R' is H or C1-4Linear or branched alkyl group) one of substituting group directly substitute and the group and linear or branched alkyl group that obtain point One or more (such as 1 to 3,1 to 2 or 1) group-CH inside minor structure <by substituting group-N < is directly substituted And the group obtained, wherein the shielding phenolic compounds at least one group R in its entire molecular structuredIt is hydrogen.
2. according to shielding phenolic compounds described in any preceding aspect, particular compound selected from the following or its arbitrary proportion Mixture:
3. a kind of steam turbine lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, antirust Agent, anti emulsifier and major amount of lube base oil, the manufacturing method of the shielding phenolic compounds include making shown in logical formula (X) Phenolic compounds and general formula (Y) shown in amine compounds sent out in the presence of aldehyde compound (preferably formaldehyde) shown in general formula (Z) The first step of raw reaction, optionally further include make the reaction product of the first step reacted with vulcanizing agent (preferably sulphur) and/or With the additional step that aldehyde compound (preferably formaldehyde) reacts shown in general formula (Z),
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain Alkyl (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), on condition that at least one A group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group is (preferably It is each independently selected from hydrogen and C1-4Linear or branched alkyl group),
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach base Group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (be preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group And C1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Straight chain or branch Alkyl group oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n1 is 1 to 8；Each cyclic groupPhase each other It is same or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- O- ,-S- and-NR'- are selected from (wherein in-NR'- R' is H or C1-4Linear or branched alkyl group) one of substituting group directly substitute and the group and linear or branched alkyl group that obtain point One or more (such as 1 to 3,1 to 2 or 1) group-CH inside minor structure <by substituting group-N < is directly substituted And the group obtained.
4. according to manufacturing method described in any preceding aspect, wherein in the first step, shown in the logical formula (X) Phenolic compounds and the general formula (Y) shown in amine compounds molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably The molar ratio of 1:0.8-2.0, aldehyde compound shown in phenolic compounds and the general formula (Z) shown in the logical formula (X) are 1: 0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8-2.0, in the additional step, amine compounds shown in the general formula (Y) The molar ratio of object and the vulcanizing agent is 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-3.0, shown in the general formula (Y) Amine compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0。
5. in the steam turbine lubricating oil composition described in any preceding aspect, the shielding phenolic compounds accounts for the steamer The 0.001%-10% of machine lubricant oil composite total weight, preferably 0.05%-5%, more preferable 0.1%-3%；
The extreme pressure anti-wear additives can be selected from olefine sulfide, phosphate derivative, phosphorothioate derivative, dialkyl group two One of thiocarbamate and dialkyl dithiophosphate are a variety of.The olefine sulfide can extensively be reached selected from Shenyang Sulfide isobutene T321A, T321B and T321C of Chemical Co., Ltd.'s production, the sulfide isobutene of Shandong east chemical fertilizer factory production T321, the Anglamol33 of Lubrizol Corp., the U.S., american exxon-Mobil Corporation Mobilad C-170 etc..The phosphoric acid Ester derivant can selected from di-n-butyl phosphite, phosphorous acid di-n-octyl, phosphorous acid diisobutyl ester, phosphorous acid di-isooctyl, One of tricresyl phosphate and phosphate amine salt are a variety of, for example Shandong Zibo Hui Hua Chemical Co., Ltd. can be selected raw T304, T306, T308 and T308B of production, the Irgalube353 etc. of BASF Corp. of Germany's production.The phosphorothioate derivative Object can be answered selected from thiophosphate, thiophosphate nitrogen containing derivative, thiophosphate ester amine salt, thiophosphate amine salt and One of boronation thiophosphate amine salt is a variety of, for example Jiangsu Danyang Bo Er petroleum additive Co., Ltd can be selected raw The T307 that the T305 of production, Shandong Zibo Hui Hua Chemical Co., Ltd. produce, the production of Tianjin Shun Neng Chemical Company SN3012 etc..The dialkyl dithiocarbamate can be selected from zinc dialkyl dithiocarbamate salt, lead salt and antimony Salt it is one or more, alkyl therein is the alkyl containing 2 to 12 carbon atoms, preferably containing 2 to 8 carbon atoms Alkyl can be ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, dissident One of base, n-octyl, 2- ethylhexyl, cyclohexyl, methylcyclopentyl are a variety of.The dialkyl dithiophosphate can To be selected from C2-12Alkyl ZDDP, is preferably selected from C3-8Alkyl ZDDP, alkyl can select ethyl, n-propyl, isopropyl, positive fourth Base, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethylhexyl, cyclohexyl and methyl ring One of amyl is a variety of.
The extreme pressure anti-wear additives are preferably selected from olefine sulfide and/or phosphorothioate derivative.The extreme pressure anti-wear additives account for The 0.01%-10% of the steam turbine lubricating oil composition gross mass, preferably 0.05%-8%, more preferable 0.1%-5%.
The metal deactivator can be selected from benzotriazole derivative and/or thiadiazoles derivative.The benzotriazole derivative 1,2,3- benzotriazole, methyl benzotriazazole, benzotriazole diakylaminomethylene derivative and benzotriazole can be selected from One of fatty amine salt is a variety of, and alkyl therein is the alkyl containing 2 to 20 carbon atoms, preferably contains 2 to 8 The alkyl of carbon atom, fatty amine are C2-20Kiber alkyl amine, preferably C6-18Kiber alkyl amine, for example Shandong Zibo Hui Huahua can be selected Work Co., Ltd produces T406, T706 and T551, the T551B of Shandong Chengwu hot Chemical Co., Ltd. production, German BASF- The Reoment 38 etc. of Ciba company production.The thiadiazoles derivative can selected from 2,5- dimercapto -1,3,4- thiadiazoles and/ Or 2,5- bis- (alkyl two is thio) thiadiazoles, alkyl therein is preferably to contain 6 containing the alkyl of 2 to 20 carbon atoms To the alkyl of 12 carbon atoms, such as the DMTD that Shandong Yantai Heng Nuo Chemical Industry Science Co., Ltd can be selected to produce, Shandong at The T561 of military hot Chemical Co., Ltd. production, the Cuvan 484 etc. of Vanderbilt company, U.S. production.
The metal deactivator is preferably selected from benzotriazole derivative.The metal deactivator accounts for the turbo-engine lube group Close the 0.01%-1%, preferably 0.02%-0.5%, more preferable 0.03%-0.3% of object gross mass.
The antirust agent can selected from one of sulfonate, alkyl imidazolidine derivatives and alkenyl succinic acid derivative or It is a variety of.The sulfonate can be selected from one of petroleum sodium sulfonate, barium mahogany sulfonate, dinonyl barium sulfonate and synthesis sulfonic acid magnesium Or it is a variety of, for example the T701 of jiangsu wuxi Yu Lian lube oil additive Co., Ltd can be selected, the limited public affairs of Guangzhou gloomyization chemical industry The T702 of department's production, the T705 of Shanghai Mead jar (unit of capacitance) moral Chemical Co., Ltd. production, Shanghai Bo great Chemical Co., Ltd. produce T707 etc..The alkyl imidazolidine derivatives can be selected from alkyl imidazoline alkenyl succinate and/or alkyl phosphoric acid imidazoline Salt, such as the T703 that Shanghai Mead jar (unit of capacitance) moral Chemical Co., Ltd. can be selected to produce etc..The alkenyl succinic acid derivative can To be selected from dodecenylsuccinic acid and/or dodecenylsuccinic acid ester, for example Mead jar (unit of capacitance) Dehua, Shanghai work can be selected limited The T746 and T747 etc. of company's production.
The antirust agent is preferably selected from alkenyl succinic acid derivative.The antirust agent accounts for the steam turbine lubricating oil composition The 0.001%-10% of gross mass, preferably 0.005%-5%, more preferable 0.01%-1%.
The anti emulsifier can select propylene oxide diamines condensation polymer, polyethylene oxide/propylene oxide block polymer, One of polyoxy alkylidene ether and polyoxyalkylene fatty acid esters are a variety of, for example can select the Nanjing connection profit limited public affairs of petrochemical industry Take charge of the T1001 and DL32 etc. of production.
The anti emulsifier is preferably selected from propylene oxide diamines condensation polymer；The anti emulsifier accounts for the turbo-engine lube The 0.001%-1% of composition gross mass, preferably 0.005%-0.5%, more preferable 0.01%-0.3%.
The lube base oil can select one of API I, II, III, IV and V class lubricating oil base oil or more Kind, for example one of mineral lubricating oil and synthetic lubricant fluid or a variety of, preferably II, III and IV class lubricating oil base can be selected from One of plinth oil is a variety of, most preferably IV class lubricating oil base oil.
Can also be added in steam turbine lubricating oil composition of the invention antioxidant, detersive, dispersing agent, pour-point depressant, One of viscosity index improver, Ashless friction modifiers and anti-foaming agent or various other lube oil additives.These additions Agent can be used alone, and can also be used with combination of two or more, and its dosage, from the conventional amount used of this field, there is no special Other restriction.
6. the manufacturing method of the steam turbine lubricating oil composition of any preceding aspect, including keep the shielding phenol, extreme pressure anti- The step of grinding agent, metal deactivator, antirust agent, anti emulsifier and the lube base oil mix.
Technical effect
Shielding phenolic compounds according to the present invention, phosphorus element-containing and metallic element, are not likely to produce ash content, are environmental-friendly The antioxidant of type.
Shielding phenolic compounds according to the present invention shows the high temperature significantly improved compared with the compound of the prior art Antioxygenic property (thermal stability) can effectively improve (high temperature) oxidation stability of such as lubricating oil.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, excellent rustless property is also exhibited further.This is not available for prior art compound.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, excellent cleansing performance (i.e. deposit generation rejection) is also exhibited further.This is the prior art It closes not available for object.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, excellent anti-wear and wear-resistant performance is also exhibited further.This is not available for prior art compound.
Steam turbine lubricating oil composition of the invention shows excellent antioxygenic property, detergent-dispersant performance energy, extreme pressure property Energy, abrasion resistance and rustless property, sufficiently meet the requirement for the steam-turbine lubrication oil product that long period uses under severe conditions.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain Justice.In case of conflict, it is subject to the definition of this specification.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the context of the present invention, statement " halogen " refers to fluorine, chlorine, bromine or iodine.
In the context of the present invention, term " alkyl " has conventionally known in the art meaning, including linear chain or branched chain Alkyl, linear chain or branched chain alkenyl, linear chain or branched chain alkynyl, naphthenic base, cycloalkenyl, cycloalkynyl radical, aryl or combinations thereof group, wherein It is preferred that linear or branched alkyl group, linear chain or branched chain alkenyl, aryl or combinations thereof group.It, specifically such as can be with as the alkyl Enumerate C1-20Alkyl, including C1-20Linear or branched alkyl group, C2-20Linear chain or branched chain alkenyl, C2-20Linear chain or branched chain alkynyl, C3-20 Naphthenic base, C3-20Cycloalkenyl, C3-20Cycloalkynyl radical, C6-20Aryl or combinations thereof group, wherein it is preferred that C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As the combination group, for example one or more C can be enumerated1-20Linear or branched alkyl group (preferably one or more C1-10Linear or branched alkyl group) and one or more C6-20Aryl (preferably one or more phenyl or naphthalene Base) group that is obtained by Direct Bonding.As the combination group, for example it can further enumerate one or more C1-10Straight chain Or branched alkyl phenyl, phenyl C1-10Linear or branched alkyl group or one or more C1-10Linear or branched alkyl group phenyl C1-10Straight chain Or branched alkyl etc., wherein more preferable C1-10Linear or branched alkyl group phenyl (such as tert-butyl-phenyl), phenyl C1-10Straight chain or branch Alkyl group (such as benzyl) or C1-10Linear or branched alkyl group phenyl C1-10Linear or branched alkyl group (such as t-butylbenzyl).
In the context of the present invention, so-called " linear chain or branched chain miscellaneous alkyl ", refers to linear or branched alkyl group molecule knot Inside structure (not including the end of main chain or any side chain in the alkyl molecule structure) one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (wherein the R' in-NR'- is H or C1-4Straight chain or Branched alkyl) one of substituting group directly substitute and inside the group that obtains or linear or branched alkyl group molecular structure (no Including the end of main chain or any side chain in the alkyl molecule structure) one or more (such as 1 to 3,1 to 2 or 1 It is a) group-CH <by substituting group-N < is directly substituted and the group of acquisition.As the substituting group, preferably-O- or-S-, more It is preferred that-S-.It is apparent that for the angle of structural stability, when there are multiple, between these substituting groups not directly Bonding.In addition, though the carbon atom number of the linear or branched alkyl group is because of group-CH2Or group-CH < accordingly subtracted by substitution It is few, but in order to state simplicity, still with the carbon atom number of the substitution foregoing description linear or branched alkyl group refer to the straight chain or The carbon atom number of branched heteroalkyl groups.As the linear chain or branched chain miscellaneous alkyl, for concrete example, C4Straight chained alkyl is such as(group indicated by arrow is not in inside molecular structure in formula, but is located In the end of main chain) it is directly substituted by a substituting group-O- by acquisition-CH2-O-CH2-CH3Or-CH2-CH2-O-CH3, referred to as For C4Linear heteroalkyl group.Alternatively, C4Branched alkyl is such as(base indicated by arrow in formula Group is not in inside molecular structure, but is in the end of main chain and side chain) it will be obtained by a substituting group-N < directly substitutionReferred to as C4Branched heteroalkyl groups.According to the present invention, as the miscellaneous alkane of the linear chain or branched chain Base, for example C can be enumerated3-20Linear chain or branched chain miscellaneous alkyl, wherein it is preferred that C3-10Linear chain or branched chain miscellaneous alkyl or C3-6Straight chain or Branched heteroalkyl groups.
In the context of the present specification, expression way " number+valence+group " or its refer to similar to term from the group It removes in corresponding foundation structure (such as chain, ring or combinations thereof etc.) and obtains after the hydrogen atom of quantity representated by the number Group preferably refers to remove on the carbon atom (preferably saturated carbon atom and/or the non-same carbon atom) contained by the structure The group obtained after the hydrogen atom of quantity representated by the number.For example, " trivalent linear or branched alkyl group " is referred to from straight The group for removing 3 hydrogen atoms on chain or branched paraffin (i.e. basic chain corresponding to the linear or branched alkyl group) and obtaining, and " divalent linear chain or branched chain miscellaneous alkyl " then refer to from the miscellaneous alkane of linear chain or branched chain (the preferably carbon atom contained by the miscellaneous alkane, or Person is further, from the non-same carbon atom) on remove 2 hydrogen atoms and the group that obtains.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration Chromatography (GPC) measurement.
In the context of the present specification, in case of no particular description, any gel permeation chromatography being related to (GPC) or the determination condition of GPC spectrogram is equal are as follows: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis Instrument；Mobile phase uses tetrahydrofuran, flow velocity 1mL/min, and chromatogram column temperature is 35 DEG C, delivery time 40min, sample quality point Number is 0.16%-0.20%.
According to the present invention, it is related to shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R is same or different to each other, each independently Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III), on condition that at least One group R is group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly- The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (I), there are multiple group R, one of group R is logical Group shown in formula (II), one in other two group R be it is described polyolefin-based, the other is hydrogen, C1-20Straight chain or branch Alkyl group (preferably C1-10Linear or branched alkyl group) or logical formula (III) shown in group.
According to embodiment of the present invention, in logical formula (I), when group R is described polyolefin-based, the polyolefin Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R' is same or different to each other, each independently Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (I), when there are multiple, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20 Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (II), in the definition of group L, group R " be selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV) Group shown in group and logical formula (V).
According to embodiment of the present invention, in logical formula (II), group R2Selected from hydrogen, C1-10Linear or branched alkyl group With group shown in logical formula (IV).
According to the present invention, in logical formula (II), when there are multiple, each group RbIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (II), when there are multiple, each group RcIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (II), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (II), when there are multiple, each group RdIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (II), when there are multiple, each cyclic group(in logical formula (II) Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (II) Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)), Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine Ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain Or branched alkyl.
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupBeing formed should Acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl is (preferably C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (III), in the definition of group L, group R " be selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV) Group and logical formula (V) shown in group.
According to embodiment of the present invention, in logical formula (III), group R2Selected from hydrogen, C1-10Linear or branched alkyl group With group shown in logical formula (IV).
According to the present invention, in logical formula (III), when there are multiple, each group RbIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RbIt is mutually the same Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (III), when there are multiple, each group RcIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RcIt is mutually the same Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (III), when there are multiple, each group RdIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (III), when there are multiple, each cyclic group(in logical formula (III) Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in logical formula (III) Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of logical formula (III) Base), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine Ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain Or branched alkyl.
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.
According to the present invention, in logical formula (IV), when there are multiple, each group RbIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (IV), when there are multiple, each group RcIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), the integer that n' is 0 to 7, preferably 0,1 or 2, on condition that n'+n≤8.According to An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical as the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when there are multiple, each group RdIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (IV), when there are multiple, each cyclic group(in logical formula (IV) Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV) Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)), Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine Ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain Or branched alkyl.
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupIt is formed The acridan ring.
According to the present invention, in logical formula (V), when there are multiple, each group R is same or different to each other, each independently Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R is mutually the same or not Together, hydrogen and C are each independently selected from1-300Linear or branched alkyl group.
According to the present invention, in logical formula (V), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly- The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (V), there are multiple group R, one of group R is institute State it is polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4Directly Chain or branched alkyl).
According to embodiment of the present invention, in logical formula (V), when group R is described polyolefin-based, the polyolefin Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), when there are multiple, each group R' is same or different to each other, each independently Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (V), group L is group
According to the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20 Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (V), in the definition of group L, group R " be selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen And C1-10Linear or branched alkyl group.
According to the present invention, in logical formula (V), two group R and a group-(S)a- L- occupies benzene in logical formula (V) respectively Three positions of residue on ring.
According to the present invention, in logical formula (V), a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula (V) shown in), it is necessary to it include structureAs phenol unit.According to a preferred embodiment of the present invention, the screen Phenolic compounds is covered in its entire molecular structure comprising at most 5, at most 3, at most 2 or at most 1 phenol units.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (II) or further as logical Formula (III) or (IV) are shown), it is necessary to it include structureAs amine unit.One according to the present invention Preferred embodiment, the shielding phenolic compounds include at most 15, at most 10, at most 8 in its entire molecular structure A, at most 6, at most 4, at most 3 or at most 2 amine units.
According to the present invention, the shielding phenolic compounds preferably at least has (preferably 2,3 in its entire molecular structure It is a or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure Have selected from least one of following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units, Cyclic groupIt is identical as the definition in logical formula (II) with group R ".
A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely A few hydrogen amine unit (1).
Specifically, to shield phenolic compoundsFor, the compound is in its entire molecule knot Include 2 phenol units and 2 amine units in structure, and includes 1 hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, for example following compound or its arbitrary proportion can be enumerated Mixture, but the present invention is not limited thereto.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can be with a kind of single shape of (pure) compound Formula exist, make or use, can also with the form of the mixture (in any proportion) of two or more of them exist, manufacture or It uses, this has no effect on the realization of effect of the present invention.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can pass through manufacturing method system below It makes, but is not limited thereto.
The manufacturing method according to the present invention, including make amination shown in phenolic compounds shown in logical formula (X) and general formula (Y) The first step to react in the presence of closing object aldehyde compound shown in general formula (Z).
According to the present invention, lead in formula (X), when there are multiple, each group R0It is same or different to each other, selects each independently From hydrogen ,-SH and C1-300Linear or branched alkyl group, on condition that at least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly- The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (X), there are multiple group R0, one of group R0Be- SH, other two group R0In one be it is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group is (preferably C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in logical formula (X), in group R0When being described polyolefin-based, the polyene Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when there are multiple, each group R' is same or different to each other, each independently Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (X), when there are multiple, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, as phenolic compounds shown in the logical formula (X), commercially available product can be directly used, it can also To be manufactured by conventionally known in the art method, it is not particularly limited.In addition, as shown in the logical formula (X) Phenolic compounds, can be used only one kind, can also be used with combination of two or more.
According to the present invention, the manufacturing method as phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl In the presence of changing catalysts, make phenolic compounds shown in general formula (X') and polyolefin (number-average molecular weight Mn 300-3000, it is excellent Select 500-2000, more preferable 500-1500) occur alkylated reaction method.
According to the present invention, in general formula (X'), group R' has and identical meaning in aforementioned formula (X).
According to the present invention, there are three group R' in general formula (X')0, one of group R'0It is-SH, another group R'0It is H, third group R'0It is hydrogen ,-SH or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (X'), at least one group R'0It is H, and group R'0 The contraposition of phenolic hydroxyl group in general formula (X').
According to the present invention, the polyolefin preferably passes through ethylene, propylene or C4-C10The homopolymerization of alpha-olefin passes through these Polyolefin obtained from two or more copolymerization in alkene.As the C4-C10Alpha-olefin, for example, can enumerate n-butene, Isobutene, n-pentene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) in these polyolefin Polymer chain contains olefinic double bond at its end.The olefinic double bond is usually with the ethenylidene of high reaction activity or vinyl Existing for form.
According to the present invention, as the polyolefin, more preferable polybutene.Unless otherwise indicated, term as used herein " polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and by 1- butylene, 2- butylene and different Pass through polymer prepared by copolymerization two or three in butylene.It the commercial product of this quasi polymer may also be containing negligible Other olefinic components of amount, but this has no effect on implementation of the invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB), also referred to as high reaction activity are poly- Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) Belonging to double bond is provided by methyl ethenylidene.
As the catalyst for alkylation reaction, for example Lewis acid catalyst can be enumerated, for example, selected from alchlor, Boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network One of object or a variety of is closed, wherein it is preferred that boron trifluoride etherate and/or boron trifluoride methanol complex compound.These Catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in the alkylated reaction, phenolic compounds shown in the polyolefin, the general formula (X'), Molar ratio between the catalyst for alkylation reaction such as can be 1:1-3:0.1-0.5, preferably 1:1.5-3:0.1-0.4, Most preferably 1:1.5-3:0.2-0.4, but is not limited thereto.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, preferably 1h-8h, most preferably 3h- 5h, but is not limited thereto.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most It is preferred that 20 DEG C -100 DEG C, but is not limited thereto.
According to the present invention, the alkylated reaction can be in the presence of a solvent.As the solvent, such as can be with Enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably Use hexane.
According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute The phenolic compounds shown.
According to the present invention, in general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and group
According to the present invention, in general formula (Y), when there are multiple, each group RbIt is same or different to each other, each independently Selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (Y), when there are multiple, each group RcIt is same or different to each other, each independently Selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (Y), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), the integer that n1 is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (Y), when there are multiple, each cyclic group(in the structure of general formula (Y) Inside is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the inside configuration of general formula (Y) It is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of general formula (Y)), wherein excellent Select phenyl ring.
According to the present invention, as amine compounds shown in the general formula (Y), commercially available product can be directly used, not There is special limitation.In addition, one kind can be used only as amine compounds shown in the general formula (Y), it can also be two kinds or more Kind is applied in combination.
According to the present invention, in general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C1-10Linear or branched alkyl group And C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C1-10Linear chain or branched chain Alkyl.
According to the present invention, as aldehyde compound shown in the general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzene Formaldehyde.
According to embodiment of the present invention, as the C1-6Aliphatic aldehyde, for example C can be enumerated1-6Straight chain or branch Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can be used its aqueous solution, Paraformaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, as aldehyde compound shown in the general formula (Z), one kind can be used only, can also two kinds or Multiple combinations use.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula (X) molar ratio of phenolic compounds shown in and amine compounds shown in the general formula (Y) is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula (X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the first step can depositing in solvent In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more With.
According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the first step, can be added without Catalyst can also be added in catalyst.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..As the organic acid catalyst, than Methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.
As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the first step There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the first step There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the first step terminates, pass through Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step Reaction mixture) in remove the volatile materials such as solvent that may be present after, can be obtained the reaction product of first step.
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the The additional step (hereinafter referred to as additional step A) that the reaction product of one step reacts with vulcanizing agent and (forms phenthazine ring).
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the The extra step that the reaction product of one step reacts with aldehyde compound shown in aforementioned formula (Z) and (forms acridan ring) Suddenly (hereinafter referred to as additional step B).
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can be only carried out, The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both it is carrying out The additional step A carries out the additional step B again when, do not have to the precedence of the additional step A and the additional step B There is special restriction, can first carry out the additional step A, carries out the additional step again after additional step A terminates B, or the additional step B is first carried out, the additional step A is carried out again after additional step B terminates.In addition, each attached Product (that is, reaction product from previous additional step) separating step can be had by adding between step, can also be without product point From step, it is not particularly limited.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A It is carried out after the first step terminates.At this point, the reaction product of the first step is as previously described from described first It is separated in the reaction mixture of step.Alternatively, the reaction product of the first step can also be straight without the separation It connects in the form of the reaction mixture of the first step for carrying out the additional step A.Alternatively, the additional step A It can be carried out after the additional step B terminates.When the additional step A after the additional step B terminates when carrying out, The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.Or The reaction product of person, the additional step B can also directly be mixed without the separation with the reaction of the additional step B The form of object is for carrying out the additional step A.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, in the extra step In rapid A, as the vulcanizing agent, for example sulphur and sulfur dichloride can be enumerated etc., wherein it is preferred that sulphur.As the sulphur, such as can To enumerate sulphur or sublimed sulfur.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step A, the general formula (Y) molar ratio of amine compounds shown in and the vulcanizing agent is generally 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5- 3.0。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can depositing in solvent In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more With.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A is generally in catalyst In the presence of carry out.As the catalyst, for example the catalyst that the prior art uses for this purpose and routinely can be enumerated, specifically Such as iodine.As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step A There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step A There are special restriction, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step A terminates, lead to Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step A is obtained it is that may be present After the volatile materials such as solvent, the reaction product of additional step A can be obtained, or can also be without the separation, directly For subsequent reaction step (than additional step B as the aforementioned).
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B (as independent step) can be carried out after the first step terminates, can also be carried out simultaneously with the first step, It is not particularly limited.When the additional step B after the first step terminates when carrying out, the first step it is anti- Product is answered to separate from the reaction mixture of the first step as previously described.Alternatively, the first step is anti- Answer product described attached for carrying out directly in the form of the reaction mixture of the first step without the separation Add step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When the additional step B exists When the additional step A is carried out after terminating, the reaction product of the additional step A is as described herein from the extra step It is separated in the reaction mixture of rapid A.Alternatively, the reaction product of the additional step A can also be straight without the separation It connects in the form of the reaction mixture of the additional step A for carrying out the additional step B.In addition, working as the additional step B When being carried out simultaneously with the first step, directly into the reaction system of the first step (such as in the first step Start or during the first step carries out) hydroformylation shown in the general formula (Z) is added according to hereinafter provided dosage Close object.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, as described Aldehyde compound shown in general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, than C can such as be enumerated1-6Linear chain or branched chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, For example its aqueous solution, paraformaldehyde or paraformaldehyde form can be used, it is not particularly limited.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, the general formula (Y) molar ratio of amine compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B is (as individual step When rapid progress) it can be in the presence of a solvent.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as second Nitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum Ether), C1-6Aliphatic alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as two Chloromethanes, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10 Amide (such as dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, It can also be used with combination of two or more.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual When step carries out) in, it can be added without catalyst, catalyst can also be added.As the catalyst, for example nothing can be enumerated Machine acid catalyst and organic acid catalyst.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc.. As the organic acid catalyst, for example methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can be enumerated etc..Make For the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual When step carries out) there is no particular limitation reaction time, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h- 6h。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual When step carries out) reaction temperature there is no particular limitation, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 ℃-120℃。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual When step carries out) terminate after, the reaction that is obtained by conventionally known separation method (such as evaporation etc.) from additional step B After removing the volatile materials such as solvent that may be present in mixture, the reaction product of additional step B, Huo Zheye can be obtained Subsequent reaction step can be directly used in without the separation (than additional step A as the aforementioned).
It is known in the art, aforementioned all reaction step (including the first step, the additional step A and The additional step B) generally carried out under the protection of inert gas atmosphere.As the inert gas, for example nitrogen can be enumerated Gas and argon gas etc., are not particularly limited.
According to the present invention, it is described shielding phenolic compounds manufacturing method in, as the first step reaction product, The reaction product of the reaction product of the additional step A or the additional step B can be a kind of single shielding phenolic compounds (for example shielding phenolic compounds shown in aforementioned formula (I)) is also possible to the mixture comprising a variety of shielding phenolic compounds.These Reaction product is all desired by the present invention, and the difference of existence form has no effect on the realization of effect of the present invention.Therefore, this theory These reaction products are collectively termed as to shielding phenolic compounds of the invention without distinction in bright book context.In consideration of it, according to The present invention, and be not present and these reaction products are further purified, or be further separated out a certain spy from these reaction products Determine the absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the further of desired effect of the present invention It is sometimes preferred for promotion, but for the present invention not necessarily.Even so, as the purifying or separation method, For example it can enumerate and the reaction product is purified or separated by the methods of column chromatography method or preparation chromatography.
According to embodiment of the present invention, the manufacturing method according to present invention shielding phenolic compounds above-mentioned is further related to The shielding phenolic compounds of manufacture.
Shielding phenolic compounds of the invention is due to showing excellent high-temperature oxidation resistance, particularly suitable as anti- Oxygen agent uses, and is used to manufacture the lubricant oil composite for expecting excellent (high temperature) oxidation stability especially as antioxidant.Mirror In this, according to embodiment of the present invention, it is related to a kind of steam turbine lubricating oil composition, it includes the present invention above-mentioned It is what shielding phenolic compounds (or mixture of its arbitrary proportion), antioxidant, ashless dispersant, metal detergent, ZDDP, organic Molybdenum, Ashless friction modifiers and lube base oil.
Embodiment
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance is evaluated
The lubricant oil composite that embodiment or comparative example are manufactured is as test specimen, using Pressurized Differential scanning amount heat examination The antioxygenic property that (PDSC) evaluates the test specimen is tested, is indicated with the oxidation induction period (unit is min) of test specimen.PDSC The temperature of test is 210 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.
(2) deposit generates rejection evaluation
The hair of simulation piston deposit is carried out using the lubricant oil composite that embodiment or comparative example manufacture as test specimen Motivation crankcase coking simulation test.This method is that coking plate analog meter is added in 300mL test specimen, is heated to 150 DEG C, adopts The aluminium sheet spilled oil for being 310 DEG C to temperature with continuation mode weighs the burnt amount generated on aluminium sheet after 6 hours, (single with sediment yield Position is mg) it indicates, simulate the deposit on piston.Coking amount is higher, and the piston detergency for representing this test specimen is poorer.
(3) extreme pressure property is evaluated
According to 12583 standard method of GB/T, the lubricant oil composite that embodiment or comparative example are manufactured is as test specimen Carry out extreme pressure property evaluation.Experimental condition be speed of mainshaft 1760r/min, 18~35 DEG C of sample temperature.Step by step from 784N open type Increase load, does a series of 10s test, measured wear scar diameter is recorded, until being sintered.It is negative to test the sintering measured Lotus evaluates the extreme pressure property of sample.
(4) wear resistance is evaluated
According to 0189 standard method of SH/T, the lubricant oil composite that embodiment or comparative example are manufactured is as test specimen Carry out wear resistance evaluation.The experimental condition of wear-resistant test is the effect of 392N (40kg) power, 75 DEG C of oil sump temperature, and heading turns Fast 1200r/min, time 60min.The wear resistance of sample is evaluated by the average value of the wear scar diameter of following three balls.
(5) high-frequency reciprocating friction test antifriction performance is evaluated
The lubricant oil composite that embodiment or comparative example manufacture is subjected to high-frequency reciprocating friction test as test specimen.It should The experimental condition of method is load 1000g, frequency 20Hz, 100 DEG C of temperature, test period 60min, records coefficient of friction.It rubs It is smaller to wipe coefficient, shows that the antifriction performance of test specimen is better.
(6) rustless property is evaluated
According to 11143 standard method of GB/T, the lubricant oil composite that embodiment or comparative example are manufactured is as test specimen Carry out antiseptic property test.300mL sample and 30mL distilled water are mixed, test rod iron is totally immersed into wherein, at 60 DEG C Stirring 24 hours, the trace of rod iron corrosion and the degree of corrosion are tested in observation after the test.
Embodiment 1
In the 500mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 58.79g is added Boron trifluoride ether (the alkylated reaction catalysis of (0.323mol) 2- tert-butyl -6- mercapto-phenol, 6.88g (0.048mol) Agent), polyisobutene (Mn=1000, the Jilin Chemical group fine chemicals of 100mL n-hexane solvent and 161.61g (0.162mol) Co., Ltd's manufacture), in 80 DEG C of reaction 2h.After reaction, reaction is cleaned using the potassium hydroxide solution that mass fraction is 5% Mixture is primary, and is washed to neutrality with hot water to remove catalyst, and then vacuum distillation removes solvent and unreacted phenol, obtains Obtain polyisobutene mercapto-phenol, hydroxyl value 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction equation is as follows:
From the nucleus magnetic hydrogen spectrum spectrum analysis of polyisobutene mercapto-phenol product: being polyisobutene at chemical shift 1.40 The characteristic peak of tert-butyl hydrogen on mercapto-phenol phenyl ring；It is unimodal for sulfydryl on polyisobutene mercapto-phenol phenyl ring at chemical shift 3.58 The characteristic peak of hydrogen；The unimodal characteristic peak for hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring at chemical shift 4.84；Chemical shift At 7.12 it is unimodal and 7.20 at it is unimodal be respectively polyisobutene mercapto-phenol phenyl ring on two hydrogen characteristic peak.By hydroxyl on phenyl ring The Definitions On Integration of hydrogen is 1, and the integral for obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, is approached Theoretical 1:1:1:1:1 is analyzed from nuclear magnetic spectrogram, has been synthesized the polyisobutene mercapto-phenol alkylation that expected contraposition replaces and has been produced Object.
Embodiment 2
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- methylphenols of addition, 9.29 grams of (112mmol) formaldehyde, 32.38 grams (176mmol) 4-aminodiphenylamine and 100mL toluene stir rapidly, in 100 DEG C of reaction 2h.To which after reaction, decompression is steamed A small amount of water of solvent and generation is removed in distillation, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (9H), 2.37 (3H), 4.02 (1H), 4.83 (2H), 6.95-7.00 (12H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 21.2,30.1,34.1,49.9,114.3,118.9,119.4,121.8, 122.2,125.8,126.5,129.5,131.8,132.3,133.5,143.3,150.8；
C24H28N2OS calculated value C 73.43, H 7.19, N 7.14, O 4.08, S 8.17；Measured value: C 73.31, H 7.23, N 7.21, O 3.99, S 8.28.
Embodiment 3
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.86 grams of (62mmol) formaldehyde, 28.15 grams (153mmol) 4-aminodiphenylamine, 0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanol stir rapidly, react at 25 DEG C 24h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained shown in title by column chromatography for separation The shielding phenol product of structure.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (18H), 3.75 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,51.2,119.4,121.8,126.5,129.5,131.4, 136.6,144.5,153.4；
C27H34N2OS calculated value C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Measured value: C 74.52, H 7.84, N 6.51, O 3.73, S 7.40.
Embodiment 4
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.24 grams of (15mmol) formaldehyde, 10.14 grams (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.23 (2H), 6.80-7.02 (10H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,117.1,121.8,126.2,129.5,136.6, 143.6,153.4；
C33H38N2OS calculated value C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Measured value: C 77.71, H 7.52, N 5.53, O 3.10, S 6.23.
Embodiment 5
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.54 grams of (115mmol) formaldehyde, 18.49 grams (69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL benzene stir rapidly, in 85 DEG C of reaction 3h.To After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H), 1.67 (2H), 3.47 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.4,29.6,34.6,45.2,52.7,58.6,119.4,121.8, 126.2,129.5,131.2,136.6,144.1,146.1,153.4；
C33H46N2OS calculated value: C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measured value: C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
Embodiment 6
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 3.57 grams of (15mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 5.14 grams of (62mmol) formaldehyde, 21.76 grams (103mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 110 DEG C of reaction 2h.To After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.20 (2H), 5.32 (1H), 6.80-7.02 (14H), 7.17 (2H), 7.20 (1H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.5,117.1,120.4,126.2,129.5,132.3, 136.6,142.8,146.1,153.4；
C36H43N3OS calculated value C 77.83, H 7.20, N 6.98, O 2.66, S 5.33；Measured value: C 77.69, H 7.19, N 7.08, O 2.65, S 5.38.
Embodiment 7
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 34.51 grams of (145mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.91 grams of (35mmol) formaldehyde, 4.49 grams (21mmol) 4- amino -4'- methoxy diphenylamine, 0.26 gram of (2.61mmol) hydrochloric acid and 150mL benzene stir rapidly, in 90 DEG C of reaction 2h.To After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.72-3.76 (4H), 4.80 (2H), 5.32 (1H), 6.97- 7.06 (8H), 7.17 (2H), 7.20 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,51.1,55.5,114.6,118.9,121.8,124.7, 126.5,132.3,136.6,144.5,153.4,154.5；
C28H36N2O2S calculated value C 72.38, H 7.81, N 6.03, O 6.89, S 6.90；Measured value: C 72.37, H 7.69, N 6.12, O 6.80, S 6.83.
Embodiment 8
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, Addition gram 21.66 (91mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.35 grams of (9.51mmol) aldehyde C-9s, 6.51 grams (25mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 70 DEG C of reaction 6h.To after reaction, subtract A small amount of water of solvent and generation is distilled off in pressure, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88 (3H), 1.08-1.85 (24H), 5.23 (1H), 5.32 (1H), 6.80 (1H), 6.97 (8H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 14.1,22.6,29.6,31.7,34.6,41.6,60.8,116.6,119.4, 121.8,126.5,129.5,131.4,136.6,142.8,144.5,146.1,153.4；
C38H48N2OS calculated value C 78.57, H 8.33, N 4.82, O 2.75, S 5.52；Measured value: C 78.62, H 8.25, N 4.75, O 2.81, S 5.42.
Embodiment 9
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 8.33 grams of (35mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 4.23 grams of (51mmol) formaldehyde, 9.61 grams of (31mmol) N, N'- diphenyl -2,6- naphthylenediamine and 150mL toluene stir rapidly, in 110 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.25 (2H), 5.32 (1H), 5.80 (1H), 6.99-7.06 (7H), 7.17 (3H), 7.26 (4H), 7.40 (2H), 7.84 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,54.8,106.9,118.6,123.3,126.2,129.2, 136.6,142.8,148.3,153.5；
C37H41N2OS calculated value C 79.24, H 7.19, N 5.00, O 2.85, S 5.72；Measured value: C 79.20, H 7.23, N 5.14, O 2.72, S 5.65.
Embodiment 10
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 6.19 grams of (26mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.57 grams of (92mmol) 3- methylthiopropionaldehyde aldehyde, 3.13 grams (17mmol) 4-aminodiphenylamine and 150mL toluene stir rapidly, in 80 DEG C of reaction 2h.To after reaction, be evaporated under reduced pressure A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (18H), 2.12-2.80 (7H), 3.47 (1H), 4.97 (1H), 5.32 (1H), 6.97 (7H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 15.2,29.6,31.9,34.6,41.7,60.2,114.3,119.4,121.8, 126.2,129.5,132.4,136.6,144.5,146.1,153.5；
C30H40N2OS2Calculated value C 70.82, H 7.92, N 5.51, O 3.14, S 12.60；Measured value: C 70.75, H 7.83, N 5.46, O 3.20, S 12.71.
Embodiment 11
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols, 4.4 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) N- are added Diphenyl-para-phenylene diamine and 150mL ethyl alcohol stir rapidly, after 60 DEG C of reaction 2.5h, are down to room temperature, 7.05 grams (85mmol) is added Formaldehyde is warming up to 85 DEG C of reaction 2.5h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column Chromatography obtains the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.74 (1H), 4.12 (2H), 4.59 (1H), 4.83 (2H), 5.32 (1H), 6.97-7.11 (5H), 7.17 (2H), 7.24 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,33.1,34.6,50.6,119.4,123.3,126.2,126.7, 127.9,136.6,140.5,142.9,153.4；
C26H34N2OS calculated value C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Measured value: C 75.20, H 7.59, N 6.29, O 3.65, S 7.22.
Embodiment 12
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.04 grams of (121mmol) formaldehyde, 19.93 grams (94mmol) 4- amino -4'- ethyl diphenylamines and 150mL dimethylbenzene stir rapidly, after 90 DEG C of reaction 3h, are down to room temperature, add Enter 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine, is warming up to 150 DEG C of reaction 8h.To after reaction, depressurize A small amount of water of solvent and generation is distilled off, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.23 (1H), 1.36 (18H), 2.61 (2H), 3.77 (1H), 4.84 (2H), 5.32 (1H), 5.70 (1H), 6.98 (5H), 7.17 (2H), 7.49 (1H)；
13C NMR (75MHz, CDCl3): δ 15.60,29.6,34.6,50.7,118.9,121.8,126.2,129.7, 136.6,141.2,146.1,153.4；
C29H36N2OS2Calculated value C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Measured value: C 70.77, H 7.41, N 5.67, O 3.17, S 12.93.
Embodiment 13
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 10.95 grams of (46mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.98 grams of (48mmol) formaldehyde, 13.78 grams (53mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL trimethylbenzene stir rapidly, after 85 DEG C of reaction 1h, are added 3.82 grams (46mmol) formaldehyde continues after 85 DEG C of reaction 1h, is down to room temperature, and 10.11 grams of (316mmol) sulphur and 0.27 gram is added (2.11mmol) iodine is warming up to 180 DEG C of reaction 1h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, and The shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 4.26 (2H), 5.18 (2H), 5.32 (1H), 6.40 (1H), 6.97 (8H), 7.17 (2H), 7.37 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,33.6,34.6,54.3,106.5,114.4,119.4,121.8, 126.2,129.5,136.6,141.9,144.5,153.4；
C34H36N2OS2Calculated value C 73.87, H 6.56, N 5.07, O 2.89, S 11.60；Measured value: C 73.91, H 6.49, N 5.02, O 2.94, S 11.49.
Embodiment 14
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.39 grams of (89mmol) formaldehyde, 6.62 grams (36mmol) 4-aminodiphenylamine, 0.45 gram of (4.51mmol) sodium hydroxide and 150mL isopropanol stir rapidly, in 80 DEG C of reaction 3h.To After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (36H), 4.82 (4H), 5.32 (2H), 6.97 (7H), 7.17 (4H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,56.5,106.5,119.4,121.8,126.5,129.5, 131.4,136.6,144.5,146.1,153.4；
C42H56N2O2S2Calculated value C 73.64, H 8.24, N 4.09, O 4.67, S 9.36；Measured value: C 73.59, H 8.21, N 4.15, O 4.62, S 9.34.
Embodiment 15
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 6.55 grams of (36mmol) 2- tert-butyl -4- mercapto-phenols, 7.64 grams of (92mmol) formaldehyde, 13.06 grams of (71mmol) N- benzene are added Base p-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To which after reaction, vacuum distillation removes solvent and life At a small amount of water, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (9H), 3.81 (1H), 4.38 (2H), 4.69 (2H), 5.29 (1H), 6.95-7.00 (15H), 7.17 (1H), 7.26 (4H), 7.55 (1H), 8.62 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,43.5,50.8,114.3,119.4,121.8,125.4, 129.5,132.3,136.6,145.2,146.1,149.0,153.4；
C36H38N4OS calculated value C 75.23, H 6.66, N 9.75, O 2.78, S 5.58；Measured value: C 75.27, H 6.69, N 9.68, O 2.79, S 5.51.
Embodiment 16
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 11.66 grams of (49mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.92 grams of (53mmol) 2,6- DI-tert-butylphenol compounds, 7.89 grams of (95mmol) formaldehyde, 11.23 grams of (32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stirs rapidly, in 100 DEG C of reaction 3h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, And the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (36H), 4.91 (2H), 5.22 (2H), 5.32 (2H), 6.97- 7.07 (16H), 7.17 (2H), 7.20 (1H), 7.27 (4H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.4,55.6,56.9,93.6,119.4,123.3,126.5, 129.2,131.4,136.6,142.8,146.1,153.4；
C54H65N3O2S calculated value C 79.08, H 7.99, N 5.12, O 3.90, S 3.91；Measured value: C 79.15, H 8.03, N 5.01, O 3.87, S 3.85.
Embodiment 17
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 47.16 grams of (45mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 4.23 grams of (51mmol) formaldehyde, 9.75 grams (53mmol) 4-aminodiphenylamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 2.5h.To after reaction, be evaporated under reduced pressure A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88,0.98,1.02,1.24,1.40,2.42,4.86,6.97,7.02, 7.14,7.26,7.55；
13C NMR (75MHz, CDCl3): δ 28.2,30.1,32.3,34.5,38.1,49.8,59.1,114.3,119.4, 121.8,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Embodiment 18
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 29.34 grams of (28mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 2.91 grams of (35mmol) formaldehyde, 6.24 grams (24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 2h.To after reaction, Vacuum distillation removes a small amount of water of solvent and generation, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88,0.98,1.02,1.24,1.40,2.42,4.00,4.86,5.56, 6.97,7.02,7.14,7.26,7.55；
13C NMR (75MHz, CDCl3): δ 28.2,30.1,32.3,33.1,34.5,38.1,49.8,59.1,114.3, 119.4,121.8,125.2,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Comparative example 1
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.22 grams of (87mmol) formaldehyde, 14.37 grams (85mmol) Diphenylamines and 150mL methanol stir rapidly, in 60 DEG C of reaction 2h.To which after reaction, vacuum distillation removes solvent and generation A small amount of water, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H), 7.27(4H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2, 136.6,150.0,153.5；
C27H33NOS calculated value C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measured value: C 77.22, H 7.89, N 3.31, O 3.83, S 7.67.
Comparative example 2
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL methanol stir rapidly, in 70 DEG C of reaction 4h.Wait react knot Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain the shielding phenol of structure shown in title by column chromatography for separation Product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H), 4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.40,24.6,30.4,34.3,45.7,54.5,56.7,116.6, 120.4,121.8,125.9,128.9,129.5,135.6,146.1,153.5,154.8；
C33H46N2O calculated value C 81.43, H 9.53, N 5.76, O 3.29；Measured value: C 81.38, H 9.51, N 5.79, O 3.31.
Comparative example 3
Under nitrogen protection atmosphere, in the 250mL four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyi) phenol of addition, 3.07 grams of (37mmol) formaldehyde, 11.71 grams (45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 4h.To after reaction, subtract A small amount of water of solvent and generation is distilled off in pressure, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32 (1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 28.7,31.1,34.3,35.7,54.1,117.1,119.4,123.3, 124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS calculated value C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measured value: C 78.27, H 7.96, N 4.98, O 2.92, S 5.83.
Comparative example 4~7
The composition of the comparative example 4~7 of antioxidant is shown in Table 1.
Table 1
The embodiment 19~28 of turbo-engine lube and the formula composition of comparative example 8~14 are shown in Table 2,3.By each group in table Point by formula composition be added to reconcile container in, 45 DEG C heating stirring 2 hours, respectively prepare obtain turbo-engine lube combination Object.
Some lube oil additives used in specific are as follows:
Extreme pressure anti-wear additives: vulcanization isoalkene, trade names T321；Thiophosphate nitrogen containing derivative, trade names T305.
Metal deactivator: dibutyl aminomethylene benzotriazole, trade names T551.
Antirust agent: dodecenylsuccinic acid, trade names T746.
Anti emulsifier: propylene oxide diamines condensation polymer, trade names T1001.
Lube base oil: II base oil 100N, polyolefin synthetic oil PAO6.
Table 2
Table 3
PDSC test, coking plate simulation test, four-ball test, high-frequency reciprocating friction test and corrosion test test result As shown in table 4.
From table 4, it can be seen that steam turbine lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, peace and quiet point Dissipate performance, extreme pressure property, preferable abrasion-resistance and lower coefficient of friction and excellent anti-corrosion ability.

Claims (19)

1. a kind of steam turbine lubricating oil composition, including shield phenolic compounds, extreme pressure anti-wear additives, metal deactivator, antirust agent, resist Emulsifier and major amount of lube base oil, the structure of the shielding phenolic compounds are as follows:
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula (II) group shown in group shown in and logical formula (III), on condition that at least one group R is group shown in logical formula (II)； Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group,
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V) Group；Each group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcEach other It is identical or different, it is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 Integer；Z is 0 to 3 integer；The integer that n is 1 to 8；The integer that n' is 0 to 7, on condition that n'+n≤8；Each group RdEach other It is identical or different, it is each independently selected from group shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same or Difference is each independently selected from phenyl ring and naphthalene nucleus, wherein two adjacent cyclic groupsEach other optionally by additional S atom and bridge the two rings N atom and form phenthazine ring, and/or, two adjacent cyclic groups Optionally pass through additional group each otherWith bridge the two rings N atom and form acridan Ring, wherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula (II) group shown in group shown in and logical formula (III)；Each group R' is same or different to each other, be each independently selected from hydrogen and C1-20Linear or branched alkyl group；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Directly Chain or branched heteroalkyl groups；A is 0 or 1, and two group R and a group-(S)a- L- occupies the residue three on phenyl ring respectively A position,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'- R' is H or C1-4Linear or branched alkyl group, the shielding phenolic compounds at least one group R in its entire molecular structuredIt is Hydrogen.
2. steam turbine lubricating oil composition described in accordance with the claim 1, which is characterized in that each group R is each independently selected from Hydrogen, C1-10Linear or branched alkyl group or number-average molecular weight Mn are group shown in polyolefin-based, the logical formula (II) of 300-3000 With group shown in logical formula (III)；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It selects each independently From hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV)；Each group RbIt is each independently selected from hydrogen and C1-10Straight chain Or branched alkyl；Each group RcIt is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen Base；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0 or 1, on condition that n'+n=1 or n'+n=2；Each group RdFor hydrogen；Each ring GroupSelected from phenyl ring.
3. steam turbine lubricating oil composition according to claim 2, which is characterized in that group R " is selected from hydrogen, C1-10Straight chain or Branched alkyl and C3-10Linear chain or branched chain miscellaneous alkyl.
4. steam turbine lubricating oil composition according to claim 2, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
5. steam turbine lubricating oil composition according to claim 2, which is characterized in that each group R is each independently selected from Hydrogen and C1-300Linear or branched alkyl group.
6. steam turbine lubricating oil composition described in accordance with the claim 1, which is characterized in that the shielding phenolic compounds be selected from Under particular compound or its arbitrary proportion mixture:
7. a kind of steam turbine lubricating oil composition, including shield phenolic compounds, extreme pressure anti-wear additives, metal deactivator, antirust agent, resist Emulsifier and major amount of lube base oil, the manufacturing method of the shielding phenolic compounds include making phenol shown in logical formula (X) The first step to react in the presence of amine compounds aldehyde compound shown in general formula (Z) shown in compound and general formula (Y) Suddenly, optionally further include make the reaction product of the first step reacted with vulcanizing agent and/or with aldehyde compound shown in general formula (Z) The additional step of reaction,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain alkane Base, on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight chain Or branched alkyl,
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach group Rb It is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcIt is same or different to each other, respectively From independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z be 0 to 3 integer；The integer that n1 is 1 to 8；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and Naphthalene nucleus,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'- R' is H or C1-4Linear or branched alkyl group.
8. steam turbine lubricating oil composition according to claim 7, which is characterized in that aldehyde compound shown in general formula (Z) For formaldehyde；The vulcanizing agent is sulphur；
Each group R0It is each independently selected from hydrogen ,-SH and C1-10Linear or branched alkyl group or number-average molecular weight Mn are 300-3000 It is polyolefin-based；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Each group RbIt is each independently selected from hydrogen and C1-10Linear or branched alkyl group；Each group RcIt is each independently selected from hydrogen, C1-10 Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic groupSelected from phenyl ring；Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl.
9. steam turbine lubricating oil composition according to claim 8, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
10. steam turbine lubricating oil composition according to claim 8, which is characterized in that group R " is selected from hydrogen, C1-10Straight chain Or branched alkyl and C3-10Linear chain or branched chain miscellaneous alkyl.
11. steam turbine lubricating oil composition according to claim 7, which is characterized in that described in the first step The molar ratio of phenolic compounds shown in logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.1-10, the general formula (X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is 1:0.1-10, in the additional step In, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1-10, amine shown in the general formula (Y) The molar ratio of compound and aldehyde compound shown in the general formula (Z) is 1:0.1-10.
12. steam turbine lubricating oil composition according to claim 7, which is characterized in that described in the first step The molar ratio of phenolic compounds shown in logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.5-5.0, the general formula (X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is 1:0.5-5.0, in the extra step In rapid, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.2-6.0, shown in the general formula (Y) Amine compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.5-5.0.
13. steam turbine lubricating oil composition according to claim 7, which is characterized in that described in the first step The molar ratio of phenolic compounds shown in logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.8-2.0, the general formula (X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is 1:0.8-2.0, in the extra step In rapid, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.5-3.0, shown in the general formula (Y) Amine compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.8-2.0.
14. according to steam turbine lubricating oil composition described in one of claim 1-13, which is characterized in that the shielding phenolate is closed Object accounts for the 0.001-10% of the steam turbine lubricating oil composition total weight；
The extreme pressure anti-wear additives are selected from olefine sulfide, phosphate derivative, phosphorothioate derivative, dialkyl dithio amino One of formates and dialkyl dithiophosphate are a variety of, Zhan Suoshu steam turbine lubricating oil composition gross mass 0.01%-10%；
The metal deactivator is selected from benzotriazole derivative and/or thiadiazoles derivative, Zhan Suoshu steam turbine lubricating oil composition The 0.01%-1% of gross mass；
The antirust agent is selected from one of sulfonate, alkyl imidazolidine derivatives and alkenyl succinic acid derivative or a variety of, accounts for The 0.001%-10% of the steam turbine lubricating oil composition gross mass；
The anti emulsifier is selected from propylene oxide diamines condensation polymer, polyethylene oxide/propylene oxide block polymer, poly (oxyalkylene) One of base ether and polyoxyalkylene fatty acid esters are a variety of, Zhan Suoshu steam turbine lubricating oil composition gross mass 0.001%-1%；
The lube base oil is selected from one of APII, II, III, IV and V class lubricating oil base oil or a variety of.
15. according to steam turbine lubricating oil composition described in one of claim 1-13, which is characterized in that the extreme pressure anti-wear additives Selected from olefine sulfide and/or phosphorothioate derivative；The metal deactivator is selected from benzotriazole derivative；The antirust agent choosing From alkenyl succinic acid derivative；The anti emulsifier is selected from propylene oxide diamines condensation polymer.
16. according to steam turbine lubricating oil composition described in one of claim 1-13, which is characterized in that the shielding phenolate is closed Object accounts for the 0.05%-5% of the steam turbine lubricating oil composition total weight；The extreme pressure anti-wear additives account for the turbo-engine lube The 0.05%-8% of composition gross mass；The metal deactivator accounts for the steam turbine lubricating oil composition gross mass 0.02%-0.5%；The antirust agent accounts for the 0.005%-5% of the steam turbine lubricating oil composition gross mass；The emulsion resistance Agent accounts for the 0.005%-0.5% of the steam turbine lubricating oil composition gross mass.
17. according to steam turbine lubricating oil composition described in one of claim 1-13, which is characterized in that the shielding phenolate is closed Object accounts for the 0.1%-3% of the steam turbine lubricating oil composition total weight；The extreme pressure anti-wear additives account for the turbo-engine lube The 0.1%-5% of composition gross mass；The metal deactivator accounts for the 0.03%- of the steam turbine lubricating oil composition gross mass 0.3%；The antirust agent accounts for the 0.01%-1% of the steam turbine lubricating oil composition gross mass；The anti emulsifier accounts for described The 0.01%-0.3% of steam turbine lubricating oil composition gross mass.
18. according to steam turbine lubricating oil composition described in one of claim 1-13, which is characterized in that moisten in the steam turbine Antioxidant, detersive, dispersing agent, pour-point depressant, viscosity index improver, Ashless friction modifiers are added in sliding oil composition and resist One of infusion is a variety of.
19. the manufacturing method of steam turbine lubricating oil composition described in one of claim 1-13, including make the shielding phenolate Close the step of object, extreme pressure anti-wear additives, metal deactivator, antirust agent, anti emulsifier and major amount of lube base oil mix.
CN201510674625.0A 2015-10-19 2015-10-19 Steam turbine lubricating oil composition and its manufacturing method Active CN106590826B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510674625.0A CN106590826B (en) 2015-10-19 2015-10-19 Steam turbine lubricating oil composition and its manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510674625.0A CN106590826B (en) 2015-10-19 2015-10-19 Steam turbine lubricating oil composition and its manufacturing method

Publications (2)

Publication Number Publication Date
CN106590826A CN106590826A (en) 2017-04-26
CN106590826B true CN106590826B (en) 2019-11-15

Family

ID=58554011

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510674625.0A Active CN106590826B (en) 2015-10-19 2015-10-19 Steam turbine lubricating oil composition and its manufacturing method

Country Status (1)

Country Link
CN (1) CN106590826B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679723B (en) * 2017-10-18 2022-05-03 中国石油化工股份有限公司 Turbine lubricating oil composition and preparation method thereof
CN115975693A (en) * 2021-10-14 2023-04-18 中国石油化工股份有限公司 Industrial lubricating oil composition and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103320198A (en) * 2012-03-22 2013-09-25 中国石油天然气股份有限公司 Thioether-containing hindered phenol antioxidant and preparation method thereof
CN103320199A (en) * 2012-03-22 2013-09-25 中国石油天然气股份有限公司 Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2598703A1 (en) * 2005-02-22 2006-08-31 Polnox Corporation Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis , performances and applications
US20080090743A1 (en) * 2006-10-17 2008-04-17 Mathur Naresh C Compounds and methods of making the compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103320198A (en) * 2012-03-22 2013-09-25 中国石油天然气股份有限公司 Thioether-containing hindered phenol antioxidant and preparation method thereof
CN103320199A (en) * 2012-03-22 2013-09-25 中国石油天然气股份有限公司 Screen phenol-containing thiadiazole type antioxygen antiwear additive and preparation method thereof

Also Published As

Publication number Publication date
CN106590826A (en) 2017-04-26

Similar Documents

Publication Publication Date Title
CN106318528B (en) Universal gear lubricating oil composition
CN106318531B (en) Diesel engine lubricating oil composite and its manufacturing method
CN106590829B (en) Railway high speed diesel engine lubricating oil composite and its manufacturing method
CN106590849B (en) Hydraulic fluid compositions and its manufacturing method
CN106590826B (en) Steam turbine lubricating oil composition and its manufacturing method
CN106318519B (en) A kind of gasoline engine oil lubricant oil composite and preparation method thereof
CN106590827B (en) Lubricant composition for four-stroke motorcycle engine and its manufacturing method
CN106590828B (en) A kind of heavy duty automobile gear lubricating oil composition and its manufacturing method
CN106590850B (en) A kind of worm and gear lubricant oil composite and its manufacturing method
CN106590833B (en) Two-stroke engine lubricating oil composition and its manufacturing method
CN106318530B (en) Lubricant composition for gasoline engine and its manufacturing method
CN106590847B (en) A kind of high-temperature chain oil composition and its manufacturing method
CN106590830B (en) A kind of fully synthetic extreme pressure lubricating oil for industrial gears composition and its manufacturing method
CN106590852B (en) A kind of industrial lubrication fluid composition and its manufacturing method
CN106590832B (en) Gas engine lubricant oil composite and its manufacturing method
CN106318525B (en) Diesel engine oil composition and its manufacturing method
CN106590848B (en) A kind of automatic drive liquid composition and its manufacturing method
CN106318546B (en) A kind of diesel engine lubricating oil composite and preparation method thereof
CN106256890B (en) Lubricant composition for gasoline engine
CN106590851B (en) Compressor lubrication fluid composition and its manufacturing method
CN106256889B (en) Diesel engine oil composition and its manufacturing method
CN106318526B (en) Methanol-fueled engine lubricant oil composite and its manufacturing method
CN106318524B (en) Composition oil of gasoline engine and its manufacturing method
CN106318529B (en) Universal gear lubricating oil composition and its manufacturing method
CN106318527B (en) Methanol-fueled engine lubricant oil composite and its manufacturing method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210714

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: China Petroleum & Chemical Corp.

Patentee after: SINOPEC CORP Research Institute OF PETROLEUM PROCESSING

Patentee after: Beijing General Fine Chemical Technology Development Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: China Petroleum & Chemical Corp.

Patentee before: SINOPEC CORP Research Institute OF PETROLEUM PROCESSING