CN106590828A - Heavy-load vehicle gear lubricating oil composition and manufacturing method thereof - Google Patents

Heavy-load vehicle gear lubricating oil composition and manufacturing method thereof Download PDF

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CN106590828A
CN106590828A CN201510674632.0A CN201510674632A CN106590828A CN 106590828 A CN106590828 A CN 106590828A CN 201510674632 A CN201510674632 A CN 201510674632A CN 106590828 A CN106590828 A CN 106590828A
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group
straight
branched alkyl
hydrogen
alkyl
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CN106590828B (en
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苏朔
龙军
段庆华
张辉
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention relates to a heavy-load vehicle gear lubricating oil composition, which comprises a screen phenol compound, a sulfur containing extreme pressure additive, a phosphor containing wear-resistant additive, a metal deactivator, an antirust agent, an ash-free friction improver, and a lubricating oil base oil accounting for the most weight of the composition; wherein the structure of the screen phenol is represented by the formula (I), and the definitions of each group of the formula (I) are shown in the description. The provided heavy-load vehicle gear lubricating oil composition can meet the high requirements on anti-oxidation performance, and also has an excellent cleaning and dispersing performance, extreme pressure property, antiwear performance, and antirust property.

Description

A kind of heavy duty automobile gear lubricating oil composition and its manufacture method
Technical field
The present invention relates to a kind of heavy duty automobile gear lubricating oil composition.Specifically, originally Invention is related to a kind of heavy duty automobile gear lubricant for meeting GL-5 and above specification requirement.
Background technology
With the raising and the increase of speed of automobile engine power, hypoid gear into For the transmission device that automobile axle is most general.The load weight of automobile hypoid gear, slip Speed is high, and the requirement of gear mesh gear oil more any than other is all high.Back axle hypoid gear The maximum operating temperature of oil is 120～130 DEG C, and modern vehicle back axle oil temperature is sometimes reachable 160℃.When automobile starts under heavy loading, climbs or run into impact load, face of gear connects There is considerable part in tactile area in boundary lubrication condition, and face of gear load may be up to 1.7GPa, Impact load may be up to 2.8GPa.Particularly high biasing hypoid gear, not only load Weight, speed are fast, and face of gear glide direction can be with contact line angulation very little, on-load fortune When turning, mainly by the extreme pressure anti-wear additives in lubricating oil friction and wear is reduced.
Work under the harsh conditions such as high speed impact load, high speed low torque or low-speed high-torque Various gears, the especially hypoid gear of various vehicles, they are to gear lubricant The requirement of combination property is very strict, not only needs gear lubricant to show excellent high temperature Antioxygenic property, extremely long service life, the bearing capacity of protrusion and resistance to marring are good, also Need with little, the excellent corrosion resistance of deposit tendentiousness, rust-preventing characteristic and demulsibility Deng.
Seek the heavy duty automobile of more efficiently antioxidant additive and exploitation novel high-performance The target that gear lubricant, always those skilled in the art are made great efforts.
United States Patent (USP) US 5304314 is disclosed and a kind of is suitable as the sulfur-bearing that antioxidant is used With the phenolic compounds of arylamine.United States Patent (USP) US 2006/0189824A1 discloses a kind of being adapted to As the shielding phenolic compounds containing secondary aromatic amine that antioxidant is used.
But, the compound of these prior arts is used in heavy duty automobile gear lubricant When, the high-temperature oxidation resistance of oil product, extreme pressure bearing capacity and abrasion resistance still exist and change Kind leeway.In addition, in addition to the adverse effect of deposit, the corruption of some key positions Erosion and corrosion can also have a strong impact on the performance of operating condition of gear train assembly, shorten its service life. Concern of the prior art to rustless property is also far from enough.
Therefore, prior art is still required for a kind of heavy duty automobile gear lubricating oil composition, It is not only able to meet current more high standard product to high-temperature oxidation resistance, extreme pressure carrying energy The increasingly harsh requirement of power and abrasion resistance, and also show excellent detergent-dispersant performance energy, Antiseptic property and rustless property.
The content of the invention
The present invention relates to the content of following aspect.
A kind of 1. heavy duty automobile gear lubricating oil composition, including shielding phenolic compounds, Sulfur-bearing EP agent, phosphorous antiwear additive, metal deactivator, antirust agent, ashless rub Wipe modifier and major amount of lube base oil；
It is described shielding phenolic compounds structure be：
In logical formula (I), each group R is same to each other or different to each other, be each independently selected from hydrogen, C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn is polyolefin-based for 300-3000), the group shown in logical formula (II) and logical formula (III) Shown group, on condition that at least one group R is the group shown in logical formula (II)；Respectively Group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkane Base (is preferably each independently selected from hydrogen and C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is mutually the same or not Together, it is independently of one another groupWherein group R " is selected from hydrogen, C1-20Hydrocarbon Base (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, preferably Selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl；Each group R2It is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl, The group shown in group and logical formula (V) shown in logical formula (IV) is (preferably independently of one another Selected from hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV))；Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Straight or branched alkyl is (excellent Choosing is each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group RcPhase each other It is same or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain Or branched alkyl epoxide (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, is more preferably in cyclic groupUpper nitrogen-atoms Contraposition)；Y is 0 to 3 integer (preferably 0 or 1)；Z be 0 to 3 integer it is (excellent Select 0 or 1)；N is 1 to 8 integer (preferably 1 or 2)；N' be 0 to 7 integer it is (excellent 0,1 or 2) is selected, on condition that n'+n≤8 (preferred n'+n=1 or n'+n=2)；Each group Rd It is same to each other or different to each other, is each independently selected from hydrogen and the group shown in logical formula (V) is (excellent Select hydrogen)；Each cyclic groupIt is same to each other or different to each other, is each independently selected from phenyl ring With naphthalene nucleus (preferred phenyl ring), wherein two adjacent cyclic groupsOptionally lead to each other Cross additional S atom and bridge the N atoms of the two rings and form phenthazine ring, and/or, Two adjacent cyclic groupsEach other optionally by additional group (wherein group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10Straight or branched alkyl) and Bridge the N atoms of the two rings and form 9,10- acridan rings,
In logical formula (V), each group R is same to each other or different to each other, be each independently selected from hydrogen, C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn is the polyolefin-based of 300-3000), the group shown in logical formula (II) and logical formula (III) institute The group for showing (is preferably each independently selected from hydrogen and C1-300Straight or branched alkyl)；Each base Group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl (preferably it is each independently selected from hydrogen and C1-4Straight or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain is propped up Alkyl group) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight chain is propped up Alkyl group and C3-10Straight or branched miscellaneous alkyl；A be 0 or 1, and two group R and One group-(S)a- L- occupies respectively three positions of residue on phenyl ring,
Wherein, the straight or branched miscellaneous alkyl is in straight or branched alkyl molecular structure One or more (such as 1 to 4,1 to 3,1 to 2 or 1) in portion Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) One of the substituting group group that directly substitutes and obtain and straight or branched alkyl molecule One or more (such as 1 to 3,1 to 2 or 1) bases of inside configuration Group-CH<By substituting group-N<The group for directly substituting and obtaining, wherein the shielding phenolate Compound at least one group R in its whole molecular structuredIt is hydrogen.
2. according to the shielding phenolic compounds described in any preceding aspect, selected from following tool The mixture of body compound or its arbitrary proportion：
A kind of 3. heavy duty automobile gear lubricating oil composition, including shielding phenolic compounds, Sulfur-bearing EP agent, phosphorous antiwear additive, metal deactivator, antirust agent, ashless rub Wipe modifier and major amount of lube base oil, the manufacturer of the shielding phenolic compounds Method includes making the phenolic compounds and the amines shown in formula (Y) shown in logical formula (X) Reacted in the presence of the aldehyde compound (preferred formaldehyde) shown in formula (Z) One step, optionally also includes making the product and vulcanizing agent (preferred sulphur) of the first step Reaction and/or the extra step with aldehyde compound (preferred formaldehyde) reaction shown in formula (Z) Suddenly,
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from Hydrogen ,-SH and C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or Number-average molecular weight Mn is polyolefin-based for 300-3000's), on condition that at least one group R0 It is-SH；Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight chain Or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen And C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight chain is propped up Alkyl group)；Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20 Straight or branched alkyl and C1-20Straight or branched alkyl epoxide (is preferably selected independently of one another From hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, 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)；N1 be 1 to 8 integer it is (excellent Select 1 or 2)；Each cyclic groupIt is same to each other or different to each other, is each independently selected from Phenyl ring and naphthalene nucleus (preferred phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain or Branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight chain or Branched alkyl and C3-10Straight or branched miscellaneous alkyl,
Wherein, the straight or branched miscellaneous alkyl is in straight or branched alkyl molecular structure One or more (such as 1 to 4,1 to 3,1 to 2 or 1) in portion Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) One of the substituting group group that directly substitutes and obtain and straight or branched alkyl molecule One or more (such as 1 to 3,1 to 2 or 1) bases of inside configuration Group-CH<By substituting group-N<The group for directly substituting and obtaining.
4. according to the manufacture method described in any preceding aspect, wherein in the first step In, the phenolic compounds shown in the logical formula (X) and the amination shown in the formula (Y) The mol ratio of compound is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, it is described Phenolic compounds shown in logical formula (X) rubs with the aldehyde compound shown in the formula (Z) You are than being 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, in the extra step In rapid, the amines shown in the formula (Y) is with the mol ratio of the vulcanizing agent 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0, the amine shown in the formula (Y) Compound is 1 with the mol ratio of the aldehyde compound shown in the formula (Z):0.1-10, it is excellent Select 1:0.5-5.0, more preferably 1:0.8-2.0.
5. in the heavy duty automobile gear lubricating oil composition described in any preceding aspect, The shielding phenolic compounds accounts for the heavy duty automobile gear lubricating oil composition gross weight 0.001%-10%, more preferably preferred 0.05%-5%, 0.1%-3%；
The sulfur-bearing EP agent can be from sulfuration more than sulfide isobutene and/or alkyl Thing.The alkyl polysulfide can be from sulfuration more than benzyldithio toluene, di-t-butyl Thing, diamyl polysulfide, 2,6 di t butyl phenol disulphide, the tertiary fourths of 2,6- bis- Base phenol trisulfide, 2,6 di t butyl phenol tetrasulfide and 2,6- di-tert-butyls One or more in phenol pentasulfide.The sulfur-bearing EP agent can be selected from Shenyang Wide sulfide isobutene T321A, T321B and T321C up to Chemical Co., Ltd.'s production, mountain The sulfide isobutene T321 of east chemical fertilizer factory production, Lubrizol Corp. of the U.S. Anglamol33, the Mobilad C-170 of american exxon-XOM etc..
The sulfur-bearing EP agent is preferably selected from sulfide isobutene；The sulfur-bearing extreme pressure adds It is excellent plus agent accounts for the 0.1%-20% of the heavy duty automobile gear lubricating oil composition gross mass Select 0.2%-10%, more preferably 0.5%-5%.
The phosphorous antiwear additive can spread out selected from phosphate derivative, thiophosphate One or more in biological and dialkyl dithiophosphate；The phosphate derivative can With selected from di-n-butyl phosphite, phosphorous acid di-n-octyl, phosphorous acid diisobutyl ester, phosphorous One or more in sour di-isooctyl, tricresyl phosphate and phosphate amine salt, such as may be used With T304, T306, T308 for being produced from Shandong Zibo Hui Hua Chemical Co., Ltd. and T308B, the Irgalube353 of BASF Corp. of Germany's production etc.；The thiophosphate Derivative can be multiple selected from thiophosphate, thiophosphate nitrogen containing derivative, D2EHDTPA One or more in ester amine salt, thiophosphate amine salt and boronation thiophosphate amine salt, T305, the mountain of the production of Jiangsu Danyang Bo Er petroleum additives Co., Ltd can such as be selected The T307 of eastern Zibo Hui Hua Chemical Co., Ltd.s production, Tianjin Shun Neng Chemical Companies SN3012 of production etc.；The dialkyl dithiophosphate can be selected from C2-12Alkyl ZDDP, is preferably selected from C3-8Alkyl ZDDP, its alkyl can from ethyl, n-propyl, It is isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, different One or more in hexyl, n-octyl, 2- ethylhexyls, cyclohexyl and methylcyclopentyl.
The phosphorous antiwear additive is preferably selected from phosphate derivative and thiophosphate spreads out Biological mixture, ratio therebetween is 1:0.5-5.The phosphorous antiwear additive is accounted for The 0.01%-10% of the heavy duty automobile gear lubricating oil composition gross mass, preferably 0.05%-8%, more preferably 0.1%-5%.
The metal deactivator can be selected from benzotriazole derivative and/or thiadiazoles derivative. The benzotriazole derivative can selected from 1,2,3- BTAs, methyl benzotriazazole, One kind in benzotriazole diakylaminomethylene derivative and benzotriazole fatty amine salt or Various, alkyl therein is the alkyl containing 2 to 20 carbon atoms, is preferably contained There is the alkyl of 2 to 8 carbon atoms, fatty amine is C2-20Kiber alkyl amine, preferred C6-18 Kiber alkyl amine, such as can select Shandong Zibo Hui Hua Chemical Co., Ltd. production T406, T706 and T551, the T551B of Shandong Chengwu hot Chemical Co., Ltd. production, German bar Reoment 38 of Si Fu-Ciba companies production etc.；The thiadiazoles derivative can be selected from 2,5- dimercapto-1,3,4-thiadiazoles and/or 2,5- bis- (alkyl two is thio) thiadiazoles, wherein Alkyl be the alkyl containing 2 to 20 carbon atoms, preferably containing 6 to 12 The alkyl of carbon atom, such as can be produced from Shandong Yantai Heng Nuo Chemical Industry Science Co., Ltd DMTD, Shandong Chengwu hot Chemical Co., Ltd. production T561, the U.S. Cuvan 484 of Vanderbilt companies production etc..
The metal deactivator is preferably selected from thiadiazoles derivative.The metal deactivator accounts for institute The 0.01%-1% of heavy duty automobile gear lubricating oil composition gross mass is stated, preferably 0.02%-0.5%, more preferably 0.03%-0.3%.
The antirust agent can be selected from the acid of sulfonate, alkyl imidazolidine derivatives and hydrocarbyl succinimide One or more in derivative.The sulfonate can be selected from petroleum sodium sulfonate, oil sulphur One or more in sour barium, dinonyl barium sulfonate and synthesis sulfonic acid magnesium, such as can select The T701 of jiangsu wuxi Yu Lian lube oil additives Co., Ltd, Guangzhou gloomyization chemical industry is limited Company production T702, Shanghai Mead jar (unit of capacitance) moral Chemical Co., Ltd. production T705, on T707 of Hai Bo great Chemical Co., Ltd.s production etc.；The alkyl imidazolidine derivatives can be with Selected from alkyl imidazoline alkenyl succinate and/or hydrocarbyl phosphate imidazoline salt, such as can be with T703 from the production of Shanghai Mead jar (unit of capacitance) moral Chemical Co., Ltd. etc.；The hydrocarbyl succinimide Acid derivative for example be able to can be selected selected from alkenyl succinic acid and/or alkenyl succinic acid ester Dodecenylsuccinic acid, dodecenylsuccinic acid ester, 17 alkenyl imidazoline alkenyl succinic acids Salt, trade names include Shanghai Mead jar (unit of capacitance) moral Chemical Co., Ltd. production T746 and T747 etc..
The antirust agent is preferably selected from hydrocarbyl succinimide acid derivative.The antirust agent accounts for described heavy The 0.001%-10% of load vehicle gear lubricating oil composition gross mass, preferably 0.005%-5%, more preferably 0.01%-1%.
The Ashless friction modifiers can select aliphatic acid, fatty acid amide, fat One or more in acid polyol ester and aliphatic amine, wherein aliphatic alkyl is carbon Saturation or unsaturated alkyl of the atomicity between 6-60, preferred carbon number is in 10-50 Between saturation or unsaturated alkyl.The aliphatic acid include leukotrienes, linoleic acid, Oleic acid, myristic acid, castor oil acid, palmitic acid, cocinic acid, laurate and tristearin Acid etc..The example of the aliphatic amide includes oleamide, coconut oleoyl amine, palmitic acid Acid amides, oleic acid diethyl amide etc..The polyol esters of fatty acids includes fatty acid glycerine Ester, fatty acid pentaerythritol ester, ethylene glycol fatty acid, aliphatic acid succinate, fat The compounds such as fat acid monoethanolamine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester Monoesters, dibasic acid esters or polyester, such as glyceryl monooleate, oleic acid diglyceride, single stearic Sour pentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, glyceryl monooleate, single linoleic acid are sweet Grease, glycerin monostearate, glyceryl monolaurate, monopalmitin, oil Sour diethanol amine, triethanolamine oleate etc.；The aliphatic amine includes that alkyl replaces unitary Amine or polyamine, the alkyl of alkoxylate replace monoamine or polyamine and alkyl ether amine etc., Such as the tallow of lauryl amine, octadecylamine, the tallow amine of ethoxylation and ethoxylation Fat ether amines.
The Ashless friction modifiers are preferably selected from polyol esters of fatty acids；It is described ashless to rub Wipe modifier and account for the heavy duty automobile gear lubricating oil composition gross mass 0.01%-5%, more preferably preferred 0.02%-4%, 0.05%-3%.
The lube base oil, can be moistened from API I, II, III, IV and V class One or more in lubricant base oil, such as can be selected from mineral lubricating oil and synthesis profit One or more in lubricating oil, in preferred II, III and IV class lubricating oil base oil Plant or various, most preferably IV class lubricating oils base oil.
Can also add in the heavy duty automobile gear lubricating oil composition of the present invention anti- Oxygen agent, detersive, dispersant, pour-point depressant, viscosity index improver, anti emulsifier and One or more in anti-foaming agent other lube oil additives.These additives can be independent Use, it is also possible to which combination of two or more is used, and its consumption is from the routine of this area Consumption, is not particularly limited.
6. the manufacturer of the heavy duty automobile gear lubricating oil composition of any preceding aspect Method, including make it is described shielding phenolic compounds, sulfur-bearing EP agent, phosphorous wear-resistant addition Agent, metal deactivator, antirust agent, Ashless friction modifiers and the lube base oil are mixed The step of conjunction.
Technique effect
Shielding phenolic compounds of the invention, phosphorus element-containing and metallic element, are not difficult to produce Raw ash content, is environmentally friendly antioxidant.
Shielding phenolic compounds of the invention, the compound phase ratio with prior art shows Go out the high-temperature oxidation resistance (heat endurance) for significantly improving, can effectively improve such as (high temperature) oxidation stability of lubricating oil.
Shielding phenolic compounds of the invention, in a preferred embodiment, is showing While excellent high-temperature oxidation resistance, excellent rustless property is also exhibited further. This is not available for prior art compound.
Shielding phenolic compounds of the invention, in a preferred embodiment, is showing While excellent high-temperature oxidation resistance, excellent cleansing performance is also exhibited further (i.e. deposit generation rejection).This is not available for prior art compound.
Shielding phenolic compounds of the invention, in a preferred embodiment, is showing While excellent high-temperature oxidation resistance, excellent antifriction antiwear is also exhibited further Energy.This is not available for prior art compound.
The heavy duty automobile gear lubricating oil composition of the present invention shows excellent anti-oxidant Performance, extreme pressure property, detergent-dispersant performance energy, abrasion resistance and rustless property, fully meet The requirement of GL-5 and above specification heavy duty automobile gear lubrication oil product.
Specific embodiment
The specific embodiment of the present invention is described in detail below, however it is necessary that point out It is that protection scope of the present invention is not limited to these specific embodiments, but by attached Claims of record are determining.
All publications, patent application, patent and other bibliography that this specification is mentioned All draw in this for reference.Unless otherwise defined, all technologies used by this specification and section Technics all has the implication that those skilled in the art routinely understand.In case of conflict, It is defined by the definition of this specification.
In the context of the present specification, in addition to the content for clearly stating, do not mention Any matters or item directly be suitable for it is known in the art those and any changing need not be carried out Become.And, any embodiment described herein can be a kind of or many with described herein Plant other embodiment freely to combine, the technical scheme or technological thought for being formed therefrom is regarded For original disclosure of the invention or a part for original description, and it is not considered as herein not The new content for disclosing or being expected, unless those skilled in the art think that the combination is substantially not Reasonably.
In the context of the present invention, state " halogen " and refer to fluorine, chlorine, bromine or iodine.
In the context of the present invention, term " alkyl " has conventionally known in the art Implication, including straight or branched alkyl, straight or branched thiazolinyl, straight or branched alkynyl, Cycloalkyl, cycloalkenyl group, cycloalkynyl radical, aryl or its combination group, wherein it is preferred that straight chain or Alkyl group, straight or branched thiazolinyl, aryl or its combination group.As the alkyl, tool Body can such as enumerate C1-20Alkyl, including C1-20Straight or branched alkyl, C2-20Straight chain Or branched-chain alkenyl, C2-20Straight or branched alkynyl, C3-20Cycloalkyl, C3-20Cycloalkenyl group, C3-20Cycloalkynyl radical, C6-20Aryl or its combination group, wherein it is preferred that C1-20Straight or branched Alkyl, C6-20Aryl or its combination group.As the combination group, such as can be with Enumerate one or more C1-20Straight or branched alkyl (preferably one or more C1-10Directly Chain or branched alkyl) and one or more C6-20Aryl (preferred one or more phenyl Or naphthyl) group that obtained by Direct Bonding.As the combination group, such as One or more C can further be enumerated1-10Straight or branched alkyl phenyl, phenyl C1-10Directly Chain or branched alkyl or one or more C1-10Straight or branched alkyl phenyl C1-10Straight chain is propped up Alkyl group etc., wherein more preferably C1-10Straight or branched alkyl phenyl (such as tert-butyl benzene Base), phenyl C1-10Straight or branched alkyl (such as benzyl) or C1-10Straight chain is propped up Alkyl group phenyl C1-10Straight or branched alkyl (such as t-butylbenzyl).
In the context of the present invention, so-called " straight or branched miscellaneous alkyl ", refers to straight chain Or branched alkyl molecular structure inside is not (including main chain or any side in the alkyl molecule structure The end of chain) one or more (such as 1 to 4,1 to 3,1 to 2 or Person 1) group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight chain or Branched alkyl) one of the substituting group group that directly substitutes and obtain or straight chain or Branched alkyl molecular structure inside is not (including main chain or any side chain in the alkyl molecule structure End) one or more (such as 1 to 3,1 to 2 or 1) bases Group-CH<By substituting group-N<The group for directly substituting and obtaining.As the replacement base Group, preferably-O- or-S-, more preferably-S-.It is apparent that from the angle of structural stability For, when having multiple, not Direct Bonding between these substituting groups.In addition, Although the carbon number of the straight or branched alkyl is because group-CH2- or group-CH<Quilt Substitute and accordingly reduce, but in order to state simplicity, still with the replacement as described before straight chain or The carbon number of branched alkyl refers to the carbon number of the straight or branched miscellaneous alkyl.As The straight or branched miscellaneous alkyl, for concrete example, C4Straight chained alkyl is such as(group in formula indicated by arrow is not in molecule Inside configuration, but in the end of main chain) by a substituting group-O- directly substitute by Acquisition-CH2-O-CH2-CH3Or-CH2-CH2-O-CH3, Referred to as C4Linear heteroalkyl group.Or, C4Branched alkyl is such as(group in formula indicated by arrow is not in molecular structure Portion, but in main chain and the end of side chain) by a substituting group-N<Directly substituting will ObtainReferred to as C4Branched heteroalkyl groups.According to the present invention, As the straight or branched miscellaneous alkyl, such as can enumerate C3-20The miscellaneous alkane of straight or branched Base, wherein it is preferred that C3-10Straight or branched miscellaneous alkyl or C3-6Straight or branched miscellaneous alkyl.
In the context of the present specification, expression way " numeral+valency+group " or it is similar Term is referred to from the foundation structure (such as chain, ring or its combination etc.) corresponding to the group It is upper remove the numeral representated by quantity hydrogen atom after obtain group, preferably refer to from On carbon atom (preferred saturated carbon atom and/or non-same carbon atom) contained by the structure The group obtained after the hydrogen atom for removing the quantity representated by the numeral.For example, " 3 Valency straight or branched alkyl " is referred to from straight or branched alkane (i.e. straight or branched alkane Basic chain corresponding to base) on remove 3 hydrogen atoms and the group that obtains, and " divalent is straight Chain or branched heteroalkyl groups " are then referred to from the miscellaneous alkane of straight or branched (preferably from the miscellaneous alkane Contained carbon atom, or further, from non-same carbon atom) on remove 2 hydrogen Atom and the group that obtains.
In the case where not clearly indicating, all percentages for being previously mentioned in this specification, Number, ratio etc. are all on the basis of weight, unless do not met this when on the basis of weight The conventional understanding of art personnel.
In the context of the present specification, in case of no particular description, the equal molecule of number Amount Mn is determined by gel permeation chromatography (GPC).
In the context of the present specification, in case of no particular description, it is any to be related to Gel permeation chromatography (GPC) or the condition determination of GPC spectrograms be：Instrument：The U.S. Waters companies waters2695 type gel osmoticing chromatogram analysis instrument；Mobile phase adopts tetrahydrochysene furan Mutter, flow velocity is 1mL/min, chromatogram column temperature is 35 DEG C, delivery time 40min, sample Mass fraction is 0.16%-0.20%.
According to the present invention, the shielding phenolic compounds being related to shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when having multiple, each group R is each other It is identical or different, it is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical formula (II) Group shown in shown group 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 C1-300Straight or branched alkyl, C can such as be enumerated1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, More preferably C1-4Straight or branched alkyl) or it is polyolefin-based.As described polyolefin-based, It is concrete such as to enumerate number-average molecular weight Mn for the polyolefin-based of 300-3000.Now, As polyolefin-based number-average molecular weight Mn, preferred 500-2000, more preferably 500-1500.According to the present invention, polyolefin-based (substantially) is that saturation (is presented For chain alkyl structure), but depending on the polyolefinic species as initiation material or this is poly- It is likely to containing a small amount of alkene in the difference of alkene manufacture method, the polyolefin-based strand Category double bond (is remained such as in polyolefin manufacturing process or introduced), but this has no effect on The realization of effect of the present invention, the present invention also has no intention to carry out clearly the amount, and the present invention Still polyolefin-based classify as this " alkyl ".
, in logical formula (I), there are multiple group R in an embodiment of the invention, One of group R is to lead to the group shown in formula (II), in two other group R It is individual be it is described polyolefin-based, another is hydrogen, C1-20Straight or branched alkyl (preferred C1-10 Straight or branched alkyl) or logical formula (III) shown in group.
An embodiment of the invention, in logical formula (I), when group R is institute When stating polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when having multiple, each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (I), when having multiple, Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane Base.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " Selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight chain is propped up Chain miscellaneous alkyl.
An embodiment of the invention, in logical formula (II), in determining for group L In justice, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched is miscellaneous Alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Straight chain is propped up Group and the group shown in logical formula (V) shown in alkyl group, logical formula (IV).
An embodiment of the invention, in logical formula (II), group R2Selected from hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (II), when having multiple, each group RbEach other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, it is preferably each From independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (II), when having multiple, Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched Alkyl, preferred hydrogen.
According to the present invention, in logical formula (II), when having multiple, each group RcEach other It is identical or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly Chain or branched alkyl epoxide.
An embodiment of the invention, in logical formula (II), when having multiple, Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched Alkyl and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (II), preferably one group RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) Contraposition.
According to the present invention, in logical formula (II), y is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in logical formula (II), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), n is 1 to 8 integer, preferably 1 or 2。
According to the present invention, in logical formula (II), when having multiple, each group RdEach other It is identical or different, it is each independently selected from hydrogen and the group shown in logical formula (V), preferred hydrogen.
According to the present invention, in logical formula (II), when having multiple, each cyclic group (being rendered as divalent group in the inside configuration of logical formula (II)) is same to each other or different to each other, respectively From independently selected from phenyl ring, (inside configuration preferably in logical formula (II) is rendered as 1,4- Asias benzene Base) and naphthalene nucleus (inside configuration preferably in logical formula (II) is rendered as 1,4- or 2,6- Asias naphthalene Base), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (II), two adjacent rings GroupCan pass through each other additional S atom (not showing in structural formula) and The N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and form fen Thiazine ring, i.e.,
The embodiment of the invention, in logical formula (II), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupBeing formed should Phenthazine ring.
An embodiment of the invention, in logical formula (II), two adjacent rings GroupAdditional group can be passed through each other(in structural formula not Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) And form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Hydrocarbon Base (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " Selected from hydrogen and C1-10Straight or branched alkyl.
The embodiment of the invention, in logical formula (II), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these ring groups GroupIn each with another adjacent cyclic groupFormed The acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " Selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight chain is propped up Chain miscellaneous alkyl.
An embodiment of the invention, in logical formula (III), in determining for group L In justice, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched is miscellaneous Alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Straight chain or Group and the group shown in logical formula (V) shown in branched alkyl, logical formula (IV).
An embodiment of the invention, in logical formula (III), group R2It is selected from Hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (III), when having multiple, each group RbThat This is identical or different, is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably It is each independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (III), when having multiple, Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched Alkyl, preferred hydrogen.
According to the present invention, in logical formula (III), when having multiple, each group RcThat This is identical or different, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20 Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (III), when having multiple, Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched Alkyl and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (III), preferably one group RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) Contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in logical formula (III), n is 1 to 8 integer, preferably 1 or 2。
According to the present invention, in logical formula (III), when having multiple, each group RdThat This is identical or different, is each independently selected from hydrogen and the group shown in logical formula (V), preferably Hydrogen.
According to the present invention, in logical formula (III), when having multiple, each cyclic group(being rendered as divalent group in the inside configuration of logical formula (III)) is mutually the same Or it is different, (inside configuration preferably in logical formula (III) is presented to be each independently selected from phenyl ring For 1,4- phenylenes) and naphthalene nucleus (inside configuration preferably in logical formula (III) is rendered as 1,4- Or 2,6- naphthylene), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (III), two adjacent rings GroupCan pass through each other additional S atom (not showing in structural formula) and The N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and form fen Thiazine ring, i.e.,
The embodiment of the invention, in logical formula (III), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupBeing formed should Phenthazine ring.
An embodiment of the invention, in logical formula (III), two adjacent rings GroupAdditional group can be passed through each other(in structural formula not Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) And form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Hydrocarbon Base (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " Selected from hydrogen and C1-10Straight or branched alkyl.
The embodiment of the invention, in logical formula (III), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these ring groups GroupIn each with another adjacent cyclic groupFormed The acridan ring.
According to the present invention, in logical formula (IV), when having multiple, each group RbThat This is identical or different, is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably It is each independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (IV), when having multiple, Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched Alkyl, preferred hydrogen.
According to the present invention, in logical formula (IV), when having multiple, each group RcThat This is identical or different, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20 Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (IV), when having multiple, Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched Alkyl and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (IV), preferably one group RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) Contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in logical formula (IV), n' is 0 to 7 integer, preferably 0,1 Or 2, on condition that n'+n≤8.An embodiment of the invention, n'+n=1 or n'+n=2. Here, n is identical with the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when having multiple, each group RdThat This is identical or different, is each independently selected from hydrogen and the group shown in logical formula (V), preferably Hydrogen.
According to the present invention, in logical formula (IV), when having multiple, each cyclic group(being rendered as divalent group in the inside configuration of logical formula (IV)) is mutually the same Or it is different, (inside configuration preferably in logical formula (IV) is presented to be each independently selected from phenyl ring For 1,4- phenylenes) and naphthalene nucleus (inside configuration preferably in logical formula (II) is rendered as 1,4- Or 2,6- naphthylene), wherein it is preferred that phenyl ring.
An embodiment of the invention, in logical formula (IV), two adjacent rings GroupCan pass through each other additional S atom (not showing in structural formula) and The N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and form fen Thiazine ring, i.e.,
The embodiment of the invention, in logical formula (IV), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupBeing formed should Phenthazine ring.
An embodiment of the invention, in logical formula (IV), two adjacent rings GroupAdditional group can be passed through each other(in structural formula not Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) And form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Hydrocarbon Base (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " Selected from hydrogen and C1-10Straight or branched alkyl.
The embodiment of the invention, in logical formula (IV), exist two with On cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these ring groups GroupIn each with another adjacent cyclic groupFormed The acridan ring.
According to the present invention, in logical formula (V), when having multiple, each group R is each other It is identical or different, it is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical formula (II) Group shown in shown group and logical formula (III).
An embodiment of the invention, in logical formula (V), when having multiple, Each group R is same to each other or different to each other, and is each independently selected from hydrogen and C1-300Straight or branched Alkyl.
According to the present invention, in logical formula (V), as the C1-300Straight or branched alkane Base, such as can enumerate C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkane Base, more preferably C1-4Straight or branched alkyl) or it is polyolefin-based.As the polyolefin Base, specifically can such as enumerate number-average molecular weight Mn for the polyolefin-based of 300-3000. Now, as polyolefin-based number-average molecular weight Mn, preferred 500-2000 is more excellent Select 500-1500.According to the present invention, polyolefin-based (substantially) is that saturation (is in It is now chain alkyl structure), but depending on the polyolefinic species as initiation material or be somebody's turn to do It is likely to containing a small amount of in the difference of polyolefin production process, the polyolefin-based strand Olefinic double bond (such as in polyolefin manufacturing process remain or introduce), but this not shadow The realization of sound effect of the present invention, the present invention also has no intention to carry out clearly the amount, and this It is bright still polyolefin-based to classify as this " alkyl ".
, in logical formula (V), there are multiple groups in an embodiment of the invention R, one of group R are described polyolefin-based, and another is hydrogen or C1-20Straight chain or Branched alkyl (preferred C1-10Straight or branched alkyl, more preferably C1-4Straight or branched alkane Base).
An embodiment of the invention, in logical formula (V), when group R is institute When stating polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), when having multiple, each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (V), when having multiple, Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane Base.
According to the present invention, in logical formula (V), group L is group
According to the present invention, in logical formula (V), in the definition of group L, group R " Selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight chain is propped up Chain miscellaneous alkyl.
An embodiment of the invention, in logical formula (V), in determining for group L In justice, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched is miscellaneous Alkyl.
According to one preferred embodiment of the invention, in logical formula (V), in group L Definition in, group R " selected from hydrogen and C1-10Straight or branched alkyl.
According to the present invention, in logical formula (V), two group R and group-(S)a-L- Three positions of residue in logical formula (V) on phenyl ring are occupied respectively.
According to the present invention, in logical formula (V), a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds is defined as previously mentioned (such as such as logical formula (I) Or further as shown in logical formula (V)), it is necessary to comprising structureAs phenol unit. According to one preferred embodiment of the invention, the shielding phenolic compounds is in its whole molecule At most 5, at most 3, at most 2 or the at most 1 phenol list are included in structure Unit.
According to the present invention, the shielding phenolic compounds is defined as previously mentioned (such as such as logical formula (II) Or further as shown in logical formula (III) or (IV)), it is necessary to comprising structureAs amine unit.According to one preferred embodiment of the invention, It is described shielding phenolic compounds in its whole molecular structure comprising at most 15, at most 10, At most 8, at most 6, at most 4, at most 3 or the at most 2 amine lists Unit.
According to the present invention, the shielding phenolic compounds in its whole molecular structure preferably at least There is (preferably 2,3 or 4 or a more) group RdIt is hydrogen.It is concrete and Speech, the shielding phenolic compounds is preferably in its whole molecular structure containing selected from following hydrogen amine At least one of unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).At these In hydrogen amine unit, cyclic groupWith group R " with logical formula (II) in definition phase Together.
A preferred embodiment of the invention, the shielding phenolic compounds is whole at its Contain hydrogen amine unit (1) described at least one in molecular structure.
Specifically, shielding phenolic compoundsAs a example by, the compound Comprising 2 phenol units and 2 amine units in its whole molecular structure, and wrap Containing 1 hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, such as can enumerate following The mixture of compound or its arbitrary proportion, but the present invention is not limited to this.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be with single In the form of a kind of (pure) compound, manufacture or use, it is also possible to two of which or In the form of various mixtures (in any proportion), manufacture or use, this not shadow The realization of sound effect of the present invention.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can by with Under manufacture method manufactured, but be not limited to this sometimes.
The manufacture method of the invention, closes including the phenolate shown in logical formula (X) is made Amines depositing in the aldehyde compound shown in formula (Z) shown in thing and formula (Y) The first step reacted under.
According to the present invention, in leading to formula (X), when having multiple, each group R0It is mutually the same or Difference, is each independently selected from hydrogen ,-SH and C1-300Straight or branched alkyl, on condition that At least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Straight or branched alkane Base, such as can enumerate C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkane Base, more preferably C1-4Straight or branched alkyl) or it is polyolefin-based.As the polyolefin Base, specifically can such as enumerate number-average molecular weight Mn for the polyolefin-based of 300-3000. Now, as polyolefin-based number-average molecular weight Mn, preferred 500-2000 is more excellent Select 500-1500.According to the present invention, polyolefin-based (substantially) is that saturation (is in It is now chain alkyl structure), but depending on the polyolefinic species as initiation material or be somebody's turn to do It is likely to containing a small amount of in the difference of polyolefin production process, the polyolefin-based strand Olefinic double bond (such as in polyolefin manufacturing process remain or introduce), but this not shadow The realization of sound effect of the present invention, the present invention also has no intention to carry out clearly the amount, and this It is bright still polyolefin-based to classify as this " alkyl ".
, in logical formula (X), there are multiple groups in an embodiment of the invention R0, one of group R0It is-SH, two other group R0In one be described poly- Alkylene, another is hydrogen or C1-20Straight or branched alkyl (preferred C1-10Straight chain is propped up Alkyl group).
An embodiment of the invention, in logical formula (X), in group R0It is institute When stating polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when having multiple, each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (X), when having multiple, Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane Base.
According to the present invention, as the phenolic compounds shown in the logical formula (X), can be direct Using commercially available product, it is also possible to manufactured by conventionally known in the art method, and Have no particular limits.In addition, as the phenolic compounds shown in the logical formula (X), can With only using one kind, it is also possible to which combination of two or more is used.
According to the present invention, as the manufacture method of the phenolic compounds shown in the logical formula (X), Such as can enumerate in the presence of catalyst for alkylation reaction, make the phenol shown in formula (X') (number-average molecular weight Mn is 300-3000, preferred 500-2000, more for compound and polyolefin It is preferred that 500-1500) occur alkylated reaction method.
According to the present invention, in formula (X'), group R' has and aforementioned formula (X) Middle identical implication.
According to three group R' of presence in the present invention, formula (X')0, one of group R'0It is-SH, another group R'0It is H, the 3rd group R'0Be hydrogen ,-SH or C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl).
An embodiment of the invention, in formula (X'), at least one group R'0It is H, and group R'0The contraposition of phenolic hydroxyl group in formula (X').
According to the present invention, the polyolefin preferably passes through ethene, propylene or C4-C10Alpha-olefin Homopolymerization or by polyolefin obtained from two or more copolymerization in these alkene.Make For the C4-C10Alpha-olefin, such as can enumerate n-butene, isobutene, n-pentene, just Hexene, positive octene and positive decene.
According to the present invention, at least 20wt% in these polyolefin (preferably at least 50wt%, More preferably at least 70wt%) polymer chain contain olefinic double bond in its end.The olefinic is double Key is usually in the form of the ethenylidene or vinyl of high reaction activity.
According to the present invention, as the polyolefin, more preferably polybutene.Unless otherwise stated, Term as used herein " polybutene " is broadly included by 1- butylene or isobutylene homopolymerisation The polymer for obtaining, and led to by two or three in 1- butylene, 2- butylene and isobutene Cross copolymerization and obtained polymer.The commercially available prod of such polymer is likely to containing negligible Other olefinic components of amount, but this has no effect on the enforcement of the present invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB), Also referred to as high-activity polyisobutylene.In this kind of polyisobutene, at least 20wt% is (excellent Choosing at least 50wt%, more preferably at least 70wt%) total terminal ethylenic double bond be by methyl What ethenylidene was provided.
As the catalyst for alkylation reaction, such as Lewis acid catalysts can be enumerated, Such as it is selected from alchlor, boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride benzene One or more in phenol, boron trifluoride alcohol complex and boron trifluoride ether complex, its In preferably boron trifluoride etherate and/or boron trifluoride methanol complex compound.These alkyl Changing catalysts can directly use commercially available product.
According to the present invention, in the alkylated reaction, the polyolefin, the formula (X') Mol ratio between shown phenolic compounds, the catalyst for alkylation reaction such as can be 1：1-3：0.1-0.5, preferably 1：1.5-3：0.1-0.4, most preferably 1：1.5-3：0.2-0.4, But this is not limited to sometimes.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, excellent 1h-8h, most preferably 3h-5h are selected, but is not limited to this sometimes.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, It is preferred that 10 DEG C -150 DEG C, most preferably 20 DEG C -100 DEG C, but this is not limited to sometimes.
According to the present invention, the alkylated reaction can be carried out in the presence of the solvent.As The solvent, such as can enumerate C6-10Alkane (such as hexane, heptane, octane, nonyl Alkane or decane etc.).Wherein, hexane and heptane are preferably used, more preferably using hexane.
According to the present invention, after the alkylated reaction terminates, by conventional methods from final Catalyst for alkylation reaction, unreacted reactant and can are removed in the reactant mixture of acquisition After the solvent that can be used, that is, obtain the phenolic compounds shown in the logical formula (X).
According to the present invention, in formula (Y), group R'2Selected from hydrogen, C1-20Straight chain or Branched alkyl and group
According to the present invention, in formula (Y), when having multiple, each group RbEach other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, it is preferably each From independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in formula (Y), when having multiple, Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched Alkyl, preferred hydrogen.
According to the present invention, in formula (Y), when having multiple, each group RcEach other It is identical or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly Chain or branched alkyl epoxide.
An embodiment of the invention, in formula (Y), when having multiple, Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched Alkyl and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in formula (Y), preferably one group RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding) Contraposition.
According to the present invention, in formula (Y), y is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in formula (Y), z is 0 to 3 integer, preferably 0 or 1。
According to the present invention, in formula (Y), n1 is 1 to 8 integer, preferably 1 or 2。
According to the present invention, in formula (Y), when having multiple, each cyclic group (being rendered as divalent group in the inside configuration of formula (Y)) is same to each other or different to each other, respectively From independently selected from phenyl ring, (inside configuration preferably in formula (Y) is rendered as 1,4- Asias benzene Base) and naphthalene nucleus (inside configuration preferably in formula (Y) be rendered as 1,4- or 2,6- Asia naphthalene Base), wherein it is preferred that phenyl ring.
According to the present invention, as the amines shown in the formula (Y), can be direct Using commercially available product, it is not particularly limited.In addition, as the formula (Y) Shown amines, can only using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in formula (Z), group R " it is selected from hydrogen, C1-20Alkyl is (excellent Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in formula (Z), group R " selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to one preferred embodiment of the invention, in formula (Z), group R " Selected from hydrogen and C1-10Straight or branched alkyl.
According to the present invention, as the aldehyde compound shown in the formula (Z), such as can be with Enumerate C1-6Aliphatic aldehyde and benzaldehyde.
An embodiment of the invention, as the C1-6Aliphatic aldehyde, such as may be used To enumerate C1-6Straight or branched saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably Formaldehyde.As the formaldehyde, such as can use its aqueous solution, paraformaldehyde or oligomeric first Aldehyde form, is not particularly limited.
According to the present invention, as the aldehyde compound shown in the formula (Z), can only make With one kind, it is also possible to which combination of two or more is used.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described first In step, the phenolic compounds shown in the logical formula (X) with shown in the formula (Y) The mol ratio of amines is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described first In step, the phenolic compounds shown in the logical formula (X) with shown in the formula (Z) The mol ratio of aldehyde compound is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of the shielding phenolic compounds, the first step Suddenly can carry out in the presence of the solvent.As the solvent, such as can enumerate C2-10 Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and Isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic Alcohol (such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20 Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Acid amides (such as dimethyl Formamide, dimethyl acetamide and 1-METHYLPYRROLIDONE) etc..These solvents can be only Using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described first In step, catalyst can be added without, it is also possible to add catalyst.As the catalyst, Inorganic acid catalyst and organic acid catalyst can such as be enumerated.As the inorganic acid catalysis Agent, such as can enumerate hydrochloric acid, sulfuric acid and phosphoric acid etc..As the organic acid catalyst, Pyrovinic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid etc. can such as be enumerated.
As the consumption of the catalyst, can directly with reference to the conventional amount used of prior art, It is not particularly limited.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described first The reaction time of step, there is no particular limitation, but generally 0.1h-24h, preferred 0.2h-12h, Most preferably 0.5h-6h.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described first There is no particular limitation for the reaction temperature of step, 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 manufacture method of the shielding phenolic compounds, described first After step terminates, by conventionally known separation method (such as evaporation etc.) from this first Remove in the reactant mixture (the hereinafter referred to as reactant mixture of first step) that step is obtained After the volatile materials such as solvent that may be present, you can obtain the product of first step.
An embodiment of the invention, the manufacture method of the shielding phenolic compounds is appointed Choosing also includes making the product of the first step and vulcanizing agent reaction (forming phenthazine ring) Additional step (hereinafter referred to as additional step A).
An embodiment of the invention, the manufacture method of the shielding phenolic compounds is appointed Choosing also includes making the product of the first step and the hydroformylation shown in aforementioned formula (Z) Additional step (the hereinafter referred to as extra step of compound reaction (formed acridan ring) Rapid B).
According to the present invention, in the manufacture method of the shielding phenolic compounds, can only carry out The additional step A, it is also possible to only carry out the additional step B, it is also possible to both carried out institute State additional step A carries out the additional step B again.Both the additional step A is being carried out When carrying out the additional step B again, to the additional step A and additional step B Precedence there is no particular limitation, can first carry out the additional step A, it is attached at this Plus step A terminates to carry out the additional step B again afterwards, or first carry out the extra step Rapid B, after additional step B terminates the additional step A is carried out again.In addition, each There can be product (that is, from the product of previous additional step) point between additional step From step, it is also possible to there is no product separating step, be not particularly limited.
An embodiment of the invention, in the manufacture method of the shielding phenolic compounds In, the additional step A is carried out after the first step terminates.Now, it is described The product of first step is as previously mentioned from the reactant mixture of the first step In separate.Or, the product of the first step can also without the separation, And be directly used to carry out the extra step in the form of the reactant mixture of the first step Rapid A.Or, the additional step A can also be after the additional step B terminates Carry out.When the additional step A after the additional step B terminates when carrying out, institute The product for stating additional step B is as described herein from the anti-of the additional step B Answer in mixture and separate.Or, the product of the additional step B can also Without the separation, and directly used in the form of the reactant mixture of the additional step B In carrying out the additional step A.
An embodiment of the invention, in the manufacture method of the shielding phenolic compounds In, in the additional step A, as the vulcanizing agent, such as can enumerate sulphur and Sulfur dichloride etc., wherein it is preferred that sulphur.As the sulphur, such as can enumerate sulphur or distillation Sulphur.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described additional In step A, the mol ratio of the amines shown in the formula (Y) and the vulcanizing agent Generally 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0.
According to the present invention, in the manufacture method of the shielding phenolic compounds, the extra step Rapid A can be carried out in the presence of the solvent.As the solvent, such as can enumerate C2-10 Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and Isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic Alcohol (such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20 Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Acid amides (such as dimethyl Formamide, dimethyl acetamide and 1-METHYLPYRROLIDONE) etc..These solvents can be only Using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in the manufacture method of the shielding phenolic compounds, the extra step Rapid A is typically carried out in the presence of a catalyst.As the catalyst, such as can lift The have technology conventional catalyst for adopting for this purpose, specifically such as iodine.As described The consumption of catalyst, can directly with reference to prior art conventional amount used, not particularly Limit.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described additional The reaction time of step A, there is no particular limitation, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described additional There is no particular limitation for the reaction temperature of step A, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described additional After step A terminates, by conventionally known separation method (such as evaporation etc.) from this The volatility thing such as solvent that may be present is removed in the reactant mixture that additional step A is obtained After matter, you can obtain the product of additional step A, or can also be without this Separate, be directly used in follow-up reactions steps (than additional step B as the aforementioned).
An embodiment of the invention, in the manufacture method of the shielding phenolic compounds In, the additional step B can be carried out (as list after the first step terminates Only step), it is also possible to carry out simultaneously with the first step, be not particularly limited. When the additional step B after the first step terminates when carrying out, the first step The separation from the reactant mixture of the first step as previously mentioned of rapid product Out.Or, the product of the first step can also be and straight without the separation To connect be used in the form of the reactant mixture of the first step and carry out the additional step B. Or, the additional step B can also be carried out after the additional step A terminates. It is described additional when the additional step B after the additional step A terminates when carrying out The reaction from the additional step A as described herein of the product of step A mixes Separate in thing.Or, the product of the additional step A can also be without The separation, and be directly used to carry out in the form of the reactant mixture of the additional step A The additional step B.In addition, when simultaneously the additional step B enters with the first step During row, directly in the reaction system of the first step (such as in the first step Start or during the first step is carried out) add institute according to hereinafter provided consumption State the aldehyde compound shown in formula (Z).
According to the present invention, in the manufacture method of the shielding phenolic compounds, described additional In step B, as the aldehyde compound shown in the formula (Z), such as can enumerate C1-6Aliphatic aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, such as can enumerate C1-6 Straight or branched saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably formaldehyde.As The formaldehyde, such as can use its aqueous solution, paraformaldehyde or paraformaldehyde form, and There is no particular limitation.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described additional In step B, the amines shown in the formula (Y) with the formula (Z) Suo Shi The mol ratio of aldehyde compound be generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0。
According to the present invention, in the manufacture method of the shielding phenolic compounds, the extra step Rapid B (when carrying out as independent step) can be carried out in the presence of the solvent.As institute Solvent is stated, such as can enumerate C2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, ring Hexane and petroleum ether), C1-6Aliphatic alcohol (such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl Alcohol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, Chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) Or C3-10Acid amides (such as dimethylformamide, dimethyl acetamide and N- methylpyrroles Alkanone) etc..These solvents can only using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in the manufacture method of the shielding phenolic compounds, described additional In step B (when carrying out as independent step), catalyst can be added without, it is also possible to Add catalyst.As the catalyst, such as can enumerate inorganic acid catalyst and organic Acid catalyst.As the inorganic acid catalyst, such as can enumerate hydrochloric acid, sulfuric acid and phosphorus Acid etc..As the organic acid catalyst, such as can enumerate pyrovinic acid, ethylsulfonic acid, Sulfamic acid and p-methyl benzenesulfonic acid etc..As the consumption of the catalyst, can directly reference The conventional amount used of prior art, is not particularly limited.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described additional The reaction time of step B (when carrying out as independent step), there is no particular limitation, but Generally 0.1h-24h, most preferably preferred 0.2h-12h, 0.5h-6h.
According to the present invention, in the manufacture method of the shielding phenolic compounds, to described additional There is no particular limitation for the reaction temperature of step B (when carrying out as independent step), 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 manufacture method of the shielding phenolic compounds, described additional After step B (when carrying out as independent step) terminates, by conventionally known separation Removing in the reactant mixture that method (such as evaporation etc.) is obtained from additional step B can After the volatile materials such as the solvent that can exist, you can the reaction for obtaining additional step B is produced Thing, or follow-up reactions steps can also be directly used in (before such as without the separation The additional step A for stating).
It is known in the art, aforementioned all of reactions steps (including the first step, The additional step A and additional step B) it is general under the protection of inert gas atmosphere Carry out.As the inert gas, such as nitrogen and argon gas etc. can be enumerated, it is not special Other restriction.
According to the present invention, in the manufacture method of the shielding phenolic compounds, as described the The product of one step, the product of the additional step A or the additional step The product of B, can be a kind of single shielding phenolic compounds (such as aforementioned formula (I) Shown shielding phenolic compounds), or the mixture comprising various shielding phenolic compounds. These product are all that desired by the present invention, the difference of its existence form has no effect on this The realization of invention effect.Therefore, in this specification context these are reacted without distinction Product is collectively termed as the shielding phenolic compounds of the present invention.In consideration of it, according to the present invention, not Presence is further purified these product, or further separates from these product The absolute necessity for going out the shielding phenolic compounds of a certain ad hoc structure.Certainly, the purifying or point It is preferred from being sometimes for the further lifting of Expected Results of the present invention, but Yu Benfa For bright not necessarily.Even so, as the purifying or separation method, such as can be with Enumerate the product is purified by methods such as column chromatography method or preparative chromatographies Or separate etc..
An embodiment of the invention, further relates to according to aforesaid shielding phenol of the invention The shielding phenolic compounds of the manufacture method manufacture of compound.
The present invention's shields phenolic compounds due to showing excellent high-temperature oxidation resistance, because This is particularly suitable as antioxidant and uses, and is used for manufacture especially as antioxidant and expects excellent (high temperature) oxidation stability lubricant oil composite.In consideration of it, of the invention one Individual embodiment, is related to a kind of heavy duty automobile gear lubricating oil composition, and it includes this Bright aforesaid any shielding phenolic compounds (or mixture of its arbitrary proportion), sulfur-bearing extreme pressure Additive, phosphorous antiwear additive, metal deactivator, antirust agent, Ashless friction modifiers With major amount of lube base oil.
Embodiment
Hereinafter the present invention is illustrated in further detail using embodiment, but the present invention is not limited to These embodiments.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance evaluation
The lubricant oil composite that embodiment or comparative example are manufactured is adopted and added as test specimen Pressure differential scanning calorimetry (PDSC) evaluates the antioxygenic property of the test specimen, to try The oxidation induction period (unit is min) for testing sample is represented.The temperature of PDSC tests is 220 DEG C, Pressure is 0.5MPa, and oxygen gas flow rate is 100mL/min.
(2) deposit generates rejection evaluation
The lubricant oil composite that embodiment or comparative example are manufactured is carried out into mould as test specimen Intend the engine crankcase coking simulated test of piston deposit.The method is by 300ml Test specimen adds coking plate analog meter, 150 DEG C is heated to, using continuation mode to temperature For 310 DEG C of aluminium sheet spilled oil, the burnt amount generated on aluminium sheet is weighed after 6 hours, to deposit Thing amount (unit is mg) expression, simulates the deposit on piston.Coking amount is higher, generation The piston detergency of table this test specimen is poorer.
(3) rustless property evaluation
According to the standard methods of GB/T 11143, the lubricating oil that embodiment or comparative example are manufactured Composition carries out antiseptic property test as test specimen.By 300mL samples and 30mL Distilled water mixes, and test rod iron is totally immersed into wherein, stirs 24 hours at 60 DEG C, The vestige of viewing test rod iron corrosion and the degree of corrosion after off-test.
(4) wear resistance evaluation
According to the standard methods of SH/T 0189, the lubricating oil group that embodiment or comparative example are manufactured Compound carries out wear resistance evaluation as test specimen.The experimental condition of wear-resistant test is The effect of 392N (40kg) power, 75 DEG C of oil sump temperature, head a ball rotating speed 1200r/min, the time 60min.The wear resistance of sample by the mean value of the wear scar diameter of following three balls come Evaluate.
(5) extreme pressure property evaluation
According to the standard methods of GB/T 12583, the lubricating oil that embodiment or comparative example are manufactured Composition carries out extreme pressure property evaluation as test specimen.Experimental condition is the speed of mainshaft 1760r/min, 18～35 DEG C of sample temperature.Increase load step by step from 784N open types, do one The 10s tests of series, the measured wear scar diameter of record, until sintering.To test survey Sintering load evaluating the extreme pressure property of sample.
(6) high-frequency reciprocating friction test antifriction performance evaluation
The lubricant oil composite that embodiment or comparative example are manufactured is carried out into height as test specimen Frequency reciprocating friction is tested.The experimental condition of the method is to load 1000g, frequency 20Hz, 100 DEG C of temperature, test period is 60min, records coefficient of friction.Coefficient of friction is less, Show that the antifriction performance of test specimen is better.
(7) copper corrosion assessment of performance is suppressed
With reference to ASTM D130 standard methods, the lubricating oil that embodiment or comparative example are manufactured Composition carries out copper strip test as test specimen.The copper sheet for having polished is immersed in into examination In sample, 121 DEG C of test temperature is heated to, is kept for 3 hours, end to be tested, take out copper Piece, it is scrubbed to be compared with Corrosion standards colour table afterwards, determine corrosion level.
Embodiment 1
In the 500ml four-hole boiling flasks equipped with agitator, thermometer, condenser pipe and dropping funel In, add 58.79g (0.323mol) the 2- tert-butyl group -6- mercapto-phenols, 6.88g (0.048mol) BFEE (catalyst for alkylation reaction), 100ml n-hexanes solvent and (Mn=1000, Jilin Chemical group fine chemicals has the polyisobutene of 161.61g (0.162mol) Limit company manufactures), react 2h at 80 DEG C.After reaction terminates, use quality fraction is 5% Potassium hydroxide solution cleaning reactant mixture once, and with hot water be washed to neutrality to remove Catalyst, then vacuum distillation removes solvent and unreacted phenol, obtains polyisobutene sulfydryl Phenol, hydroxyl value is 53.49mgKOH/g.Hydroxy value measuring is with reference in GB/T7383-2007 Acetic anhydride method.
Example reaction equation is as follows：
From the nucleus magnetic hydrogen spectrum spectrum analysis of polyisobutene mercapto-phenol product：Chemical shift It is the characteristic peak of tert-butyl group hydrogen on polyisobutene mercapto-phenol phenyl ring at 1.40；Chemical shift The unimodal characteristic peak for sulfydryl hydrogen on polyisobutene mercapto-phenol phenyl ring at 3.58；Chemical shift The unimodal characteristic peak for hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring at 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.It is 1 by the Definitions On Integration of hydroxyl hydrogen on phenyl ring, obtains hydrogen on phenyl ring, sulfydryl The integration of hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, it is close to theoretical 1:1:1:1:1, From nuclear magnetic spectrogram analysis, the polyisobutene mercapto-phenol alkyl that expected contraposition replaces is synthesized Change product.
Embodiment 2
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- Methylphenol, 9.29 grams of (112mmol) formaldehyde, 32.38 grams of (176mmol) N- benzene Base p-phenylenediamine and 100mL toluene, rapid stirring, at 100 DEG C 2h is reacted.Question response After end, vacuum distillation removes solvent and a small amount of water for generating, and is obtained by column chromatography for separation To the shielding phenol product of structure shown in title.
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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 31.65 grams of (133mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 1.86 grams of (62mmol) formaldehyde, 28.15 grams of (153mmol) N- phenyl P-phenylenediamine, 0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanols, rapid stirring, 24h is reacted at 25 DEG C.After question response terminates, it is a small amount of with what is generated that vacuum distillation removes solvent 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 1.36-1.54 (18H), 3.75 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,51.2,119.4,121.8, 126.5,129.5,131.4,136.6,144.5,153.4；
C27H34N2OS calculated values C 74.61, H 7.88, N 6.45, O 3.68, S 7.38； Measured value：C 74.52, H 7.84, N 6.51, O 3.73, S 7.40.
Embodiment 4
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 8.57 grams of (36mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 1.24 grams of (15mmol) formaldehyde, 10.14 grams of (39mmol) N, N'- bis- Phenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, rapid stirring, at 90 DEG C 4h is reacted.Treat anti- After should terminating, vacuum distillation removes solvent and a small amount of water for generating, and by column chromatography for separation Obtain 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), 5.23 (2H), 6.80-7.02 (10H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.2,117.1,121.8, 126.2,129.5,136.6,143.6,153.4；
C33H38N2OS calculated values C 77.60, H 7.50, N 5.48, O 3.13, S 6.28； Measured value：C 77.71, H 7.52, N 5.53, O 3.10, S 6.23.
Embodiment 5
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 20.23 grams of (85mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 9.54 grams of (115mmol) formaldehyde, 18.49 grams of (69mmol) N- (1,3- Dimethylbutyl)-N'- diphenyl-para-phenylene diamines and 150mL benzene, rapid stirring is anti-at 85 DEG C Answer 3h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, and leads to Cross the shielding phenol product that column chromatography for separation obtains structure shown in title.
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 values:C 76.40, H 8.94, N 5.40, O 3.08, S 6.18； Measured value：C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
Embodiment 6
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 3.57 grams of (15mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 5.14 grams of (62mmol) formaldehyde, 21.76 grams of (103mmol) N- phenyl - N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, rapid stirring, 2h is reacted at 110 DEG C.After question response terminates, it is a small amount of with what is generated that vacuum distillation removes solvent 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), 5.20 (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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 34.51 grams of (145mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 2.91 grams of (35mmol) formaldehyde, 4.49 grams of (21mmol) 4- amino -4'- Methoxy diphenylamine, 0.26 gram of (2.61mmol) hydrochloric acid and 150mL benzene, rapid stirring, 2h is reacted at 90 DEG C.After question response terminates, it is a small amount of with what is generated that vacuum distillation removes solvent 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), 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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add gram 21.66 (91mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 1.35 grams of (9.51mmol) aldehyde C-9s, 6.51 grams of (25mmol) N, N'- bis- Phenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene, rapid stirring, at 70 DEG C 6h is reacted.Question response After end, vacuum distillation removes solvent and a small amount of water for generating, and is obtained by column chromatography for separation To the shielding phenol product of structure shown in title.
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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 8.33 grams of (35mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 4.23 grams of (51mmol) formaldehyde, 9.61 grams of (31mmol) N, N'- hexichol Base -2,6- naphthylenediamines and 150mL toluene, rapid stirring, at 110 DEG C 4h is reacted.Treat anti- After should terminating, vacuum distillation removes solvent and a small amount of water for generating, and by column chromatography for separation Obtain 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), 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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 6.19 grams of (26mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 9.57 grams of (92mmol) 3- methylthiopropionaldehyde aldehyde, 3.13 grams (17mmol) 4-aminodiphenylamine and 150mL toluene, rapid stirring, at 80 DEG C 2h is reacted.Treat After reaction terminates, vacuum distillation removes solvent and a small amount of water for generating, and by column chromatography point From the shielding phenol product for obtaining structure shown in title.
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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 4.99 grams of (21mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 4.4 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) N- phenyl pair Phenylenediamine and 150mL ethanol, rapid stirring after reacting 2.5h at 60 DEG C, is down to room temperature, 7.05 grams of (85mmol) formaldehyde are added, 85 DEG C of reaction 2.5h are warming up to.Question response terminates Afterwards, vacuum distillation removes solvent and a small amount of water for generating, and is marked by column chromatography for separation The shielding phenol product of structure shown in topic.
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 values C 75.29, H 7.67, N 6.27, O 3.58, S 7.18； Measured value：C 75.20, H 7.59, N 6.29, O 3.65, S 7.22.
Embodiment 12
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 19.52 grams of (82mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 10.04 grams of (121mmol) formaldehyde, 19.93 grams of (94mmol) 4- amino - 4'- ethyls diphenylamines and 150mL dimethylbenzene, rapid stirring, after reacting 3h at 90 DEG C, Room temperature is down to, 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine is added, It is warming up to 150 DEG C of reaction 8h.After question response terminates, vacuum distillation removes solvent with 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 1.23 (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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 10.95 grams of (46mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 3.98 grams of (48mmol) formaldehyde, 13.78 grams of (53mmol) N, N'- bis- Phenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL trimethylbenzenes, rapid stirring, after reacting 1h at 85 DEG C, 3.82 grams of (46mmol) formaldehyde are added, after continuing to react 1h at 85 DEG C, room temperature is down to, 10.11 grams of (316mmol) sulphur and 0.27 gram of (2.11mmol) iodine are added, 180 DEG C are warming up to Reaction 1h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 21.66 grams of (91mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 7.39 grams of (89mmol) formaldehyde, 6.62 grams of (36mmol) N- phenyl pair Phenylenediamine, 0.45 gram of (4.51mmol) NaOH and 150mL isopropanols, stir rapidly Mix, at 80 DEG C 3h is reacted.After question response terminates, vacuum distillation removes solvent with 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 1.36-1.54 (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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 6.55 grams of (36mmol) 2- tert-butyl group -4- sulfydryl benzene Phenol, 7.64 grams of (92mmol) formaldehyde, 13.06 grams of (71mmol) N- phenyl are to benzene two Amine and 150mL toluene, rapid stirring, at 90 DEG C 4h is reacted.After question response terminates, subtract Pressure is distilled off solvent and a small amount of water for generating, 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 (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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 11.66 grams of (49mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 10.92 grams of (53mmol) 2,6- DI-tert-butylphenol compounds, 7.89 grams (95mmol) Formaldehyde, 11.23 grams of (32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitraes- Phenylenediamine and 150mL toluene, rapid stirring, at 100 DEG C 3h is reacted.Question response terminates Afterwards, vacuum distillation removes solvent and a small amount of water for generating, and is marked by column chromatography for separation The shielding phenol product of structure shown in topic.
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 values 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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 47.16 grams of (45mmol) polyisobutene mercapto-phenols (embodiment 1 is manufactured), 4.23 grams of (51mmol) formaldehyde, 9.75 grams (53mmol) 4-aminodiphenylamine and 150mL benzene, rapid stirring, at 80 DEG C 2.5h is reacted.Treat anti- After should terminating, vacuum distillation removes solvent and a small amount of water for generating, and by column chromatography for separation Obtain the shielding phenol product of structure shown in title.
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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 29.34 grams of (28mmol) polyisobutene mercapto-phenols (embodiment 1 is manufactured), 2.91 grams of (35mmol) formaldehyde, 6.24 grams (24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, rapid stirring, in 90 DEG C of reactions 2h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, and by post Chromatography obtains the shielding phenol product of structure shown in title.
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, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 20.23 grams of (85mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 7.22 grams of (87mmol) formaldehyde, 14.37 grams of (85mmol) diphenylamines With 150mL methyl alcohol, rapid stirring, at 60 DEG C 2h is reacted.After question response terminates, decompression Solvent and a small amount of water for generating are distilled off, and obtain being tied 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 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H), 7.27 (4H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.2,120.4,123.3, 125.9,126.2,129.2,136.6,150.0,153.5；
C27H33NOS calculated values C 77.28, H 7.93, N 3.34, O 3.81, S 7.64； Measured value：C 77.22, H 7.89, N 3.31, O 3.83, S 7.67.
Comparative example 2
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 10.71 grams of (52mmol) 2,6- di-t-butyl -4- Mercapto-phenol, 1.89 grams of (63mmol) formaldehyde, 17.42 grams of (65mmol) N- (1,3- Dimethylbutyl)-N'- diphenyl-para-phenylene diamines and 150mL methyl alcohol, rapid stirring, at 70 DEG C Reaction 4h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, 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 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H), 4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 17.9,22.40,24.6,30.4,34.3, 45.7,54.5,56.7,116.6,120.4,121.8,125.9,128.9,129.5,135.6, 146.1,153.5,154.8；
C33H46N2O calculated values C 81.43, H 9.53, N 5.76, O 3.29；Measured value： C 81.38, H 9.51, N 5.79, O 3.31.
Comparative example 3
Under nitrogen protection atmosphere, equipped with agitator, thermometer, condenser pipe and dropping funel 250ml four-hole boiling flasks in, add 9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- Mercaptopropyi) phenol, 3.07 grams of (37mmol) formaldehyde, 11.71 grams (45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene, rapid stirring, at 80 DEG C 4h is reacted. After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, and by column chromatography The shielding phenol product of structure shown in isolated title.
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 values C 78.22, H 8.02, N 5.07, O 2.89, S 5.80； Measured value：C 78.27, H 7.96, N 4.98, O 2.92, S 5.83.
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 heavy duty automobile gear lubricant and matching somebody with somebody for comparative example 8～14 Fang Zucheng is shown in Table 2,3.Formula composition in table is added in mediation container, at 45 DEG C Heating stirring 2 hours, prepares obtain GL-5 rank heavy duty automobile gear lubricant respectively Composition.
Some lube oil additives for specifically being used are as follows：
Sulfur-bearing EP agent：Sulfuration isoalkene, trade names T321.
Phosphorous antiwear additive：Di-n-butyl phosphite, trade names T304；It is thio The multiple ester amine salt of phosphoric acid, trade names T307.
Metal deactivator：2,5- double (octyl group two is thio) thiadiazoles, trade names T561.
Antirust agent：Dodecenylsuccinic acid, trade names T746.
Ashless friction modifiers：Glyceryl monooleate.
Lube base oil：Base oil 150SN, polyolefin artificial oil PAO6.
Table 2
Table 3
PDSC tests, coking simulated test, four-ball test, high-frequency reciprocating friction test, corrosion examination Test as shown in table 4 with the test result of copper strip test.
Table 4
From table 4, it can be seen that heavy duty automobile gear lubricating oil composition of the present invention has excellent height Warm antioxygenic property, detergent-dispersant performance energy, the bearing capacity of protrusion, excellent abrasion-resistance and relatively low Coefficient of friction and excellent resistance to corrosion and anti-corrosion ability.

Claims (10)

1. a kind of heavy duty automobile gear lubricating oil composition, including shielding phenolic compounds, sulfur-bearing pole Pressure additive, phosphorous antiwear additive, metal deactivator, antirust agent, Ashless friction modifiers and master The lube base oil to be measured, the structure of the shielding phenolic compounds is：
In logical formula (I), each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300 Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000's is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III), On condition that at least one group R is the group shown in logical formula (II)；Each group R' is mutually the same or not Together, hydrogen and C are each independently selected from1-20Straight or branched alkyl (is preferably each independently selected from hydrogen And C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other, respectively From being independently groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20 Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight chain or Branched alkyl and C3-10Straight or branched miscellaneous alkyl；Each group R2It is same to each other or different to each other, each solely On the spot it is selected from hydrogen, C1-20Group and logical formula (V) shown in straight or branched alkyl, logical formula (IV) Shown group (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and logical formula (IV) Shown group)；Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Directly Chain or branched alkyl (are preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly Chain or branched alkyl epoxide (are preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10 Straight or branched alkyl epoxide, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；y It is 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；N is 1 To 8 integer (preferably 1 or 2)；N' is 0 to 7 integer (preferably 0,1 or 2), on condition that N'+n≤8 (preferred n'+n=1 or n'+n=2)；Each group RdIt is same to each other or different to each other, independently of one another Selected from the group (preferred hydrogen) shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same Or it is different, phenyl ring and naphthalene nucleus (preferred phenyl ring) are each independently selected from, wherein two adjacent ring groups GroupOptionally formed by the S atom for adding and the N atoms for bridging the two rings each other Phenthazine ring, and/or, two adjacent cyclic groupsEach other optionally by additional group(wherein group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) And C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10Straight or branched alkyl) and bridge joint The N atoms of the two rings and form 9,10- acridan rings,
In logical formula (V), each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300 Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000 It is polyolefin-based), the group shown in logical formula (II) and the group shown in logical formula (III) (preferably each solely On the spot selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' is same to each other or different to each other, each solely On the spot selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight chain Or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Hydrocarbon Base (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, be preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl；A is 0 or 1, and two bases R and group-(S) of groupa- L- occupies respectively three positions of residue on phenyl ring,
Wherein, the straight or branched miscellaneous alkyl is selected from inside straight or branched alkyl molecular structure Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- quilt Selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of substituting group One or more inside the group for directly substituting and obtaining and straight or branched alkyl molecular structure (such as 1 to 3,1 to 2 or 1) group-CH<By substituting group-N<Directly replace Generation and obtain group, wherein the shielding phenolic compounds in its whole molecular structure at least one Group RdIt is hydrogen.
2., according to the heavy duty automobile gear lubricating oil composition described in claim 1, its feature exists In mixture of the shielding phenolic compounds selected from following particular compound or its arbitrary proportion：
3. a kind of heavy duty automobile gear lubricating oil composition, including shielding phenolic compounds, sulfur-bearing pole Pressure additive, phosphorous antiwear additive, metal deactivator, antirust agent, Ashless friction modifiers and master The lube base oil to be measured, the manufacture method of the shielding phenolic compounds includes making logical formula (X) Amines shown in shown phenolic compounds and formula (Y) is closed in the hydroformylation shown in formula (Z) The first step reacted in the presence of thing (preferred formaldehyde), optionally also includes making the first step Rapid product react with vulcanizing agent (preferred sulphur) and/or with the aldehyde compound shown in formula (Z) The additional step of (preferred formaldehyde) reaction,
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from hydrogen ,-SH And C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight Mn For the polyolefin-based of 300-3000), on condition that at least one group R0It is-SH；Each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably each independent Ground is selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20 Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each base Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20 Straight or branched alkyl epoxide (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)； Y is 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；n1 For 1 to 8 integer (preferably 1 or 2)；Each cyclic groupIt is same to each other or different to each other, respectively From independently selected from phenyl ring and naphthalene nucleus (preferred phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkane Base) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10 Straight or branched miscellaneous alkyl,
Wherein, the straight or branched miscellaneous alkyl is selected from inside straight or branched alkyl molecular structure Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- quilt Selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of substituting group One or more inside the group for directly substituting and obtaining and straight or branched alkyl molecular structure (such as 1 to 3,1 to 2 or 1) group-CH<By substituting group-N<Directly replace Generation and obtain group.
4., according to the heavy duty automobile gear lubricating oil composition described in claim 3, its feature exists In, in the first step, the phenolic compounds shown in the logical formula (X) and the formula (Y) The mol ratio of shown amines is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, Phenolic compounds shown in the logical formula (X) and the aldehyde compound shown in the formula (Z) mole Than for 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, in the additional step, institute The amines and the mol ratio of the vulcanizing agent stated shown in formula (Y) is 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0, the amines and the formula shown in the formula (Y) (Z) mol ratio of the aldehyde compound shown in is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
5. according to the heavy duty automobile gear lubricating oil composition described in one of claim 1-4, its It is characterised by, it is total that the shielding phenolic compounds accounts for the heavy duty automobile gear lubricating oil composition The 0.001-10% of weight；
The sulfur-bearing EP agent accounts for described selected from sulfide isobutene and/or alkyl polysulfide The 0.1%-20% of heavy duty automobile gear lubricating oil composition gross mass；
The phosphorous antiwear additive is selected from phosphate derivative, phosphorothioate derivative and dioxane One or more in base dithiophosphates, accounts for the heavy duty automobile gear lubricating oil composition total The 0.01%-10% of quality；
The metal deactivator accounts for described heavy selected from benzotriazole derivative and/or thiadiazoles derivative The 0.01%-1% of load vehicle gear lubricating oil composition gross mass；
The antirust agent is in sulfonate, alkyl imidazolidine derivatives and hydrocarbyl succinimide acid derivative One or more, account for the 0.001%-10% of the heavy duty automobile gear lubricating oil composition gross mass；
The Ashless friction modifiers select aliphatic acid, fatty acid amide, fatty polyol One or more in ester and aliphatic amine, accounts for the heavy duty automobile gear lubricating oil composition total The 0.01%-5% of quality；
The lube base oil is in API I, II, III, IV and V class lubricating oil base oils One or more.
6., according to the heavy duty automobile gear lubricating oil composition described in claim 5, its feature exists In the sulfur-bearing EP agent is selected from sulfide isobutene；The phosphorous antiwear additive is selected from phosphorus The mixture of acid ester derivant and phosphorothioate derivative, ratio therebetween is 1:0.5-5；Institute Metal deactivator is stated selected from thiadiazoles derivative；The antirust agent is selected from hydrocarbyl succinimide acid derivative； The Ashless friction modifiers selected fatty acid polyol ester.
7., according to the heavy duty automobile gear lubricating oil composition described in claim 5, its feature exists In the sulfur-bearing EP agent accounts for the heavy duty automobile gear lubricating oil composition gross mass 0.2%-10%；The phosphorous antiwear additive accounts for the heavy duty automobile gear lubricating oil composition The 0.05%-8% of gross mass；The metal deactivator accounts for the heavy duty automobile gear lubricant combination The 0.02%-0.5% of thing gross mass；The antirust agent accounts for the heavy duty automobile gear lubricant combination The 0.005%-5% of thing gross mass；The Ashless friction modifiers account for the heavy duty automobile gear profit The 0.02%-4% of sliding oil composition gross mass.
8., according to the heavy duty automobile gear lubricating oil composition described in claim 5, its feature exists In the sulfur-bearing EP agent accounts for the heavy duty automobile gear lubricating oil composition gross mass 0.5%-5%；The phosphorous antiwear additive accounts for the heavy duty automobile gear lubricating oil composition The 0.1%-5% of gross mass；The metal deactivator accounts for the heavy duty automobile gear lubricant combination The 0.03%-0.3% of thing gross mass；The antirust agent accounts for the heavy duty automobile gear lubricant combination The 0.01%-1% of thing gross mass；The Ashless friction modifiers account for the heavy duty automobile gear lubrication The 0.05%-3% of fluid composition gross mass.
9., according to the heavy duty automobile gear lubricating oil composition described in claim 5, its feature exists In addition antioxidant, detersive, dispersion in the heavy duty automobile gear lubricating oil composition One or more in agent, pour-point depressant, viscosity index improver, anti emulsifier and anti-foaming agent.
10. the manufacture of the heavy duty automobile gear lubricating oil composition described in one of claim 1-4 Method, including make it is described shielding phenolic compounds, sulfur-bearing EP agent, phosphorous antiwear additive, The step of metal deactivator, antirust agent, Ashless friction modifiers and the lube base oil mix.
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