CN106318527B

CN106318527B - Methanol-fueled engine lubricant oil composite and its manufacturing method

Info

Publication number: CN106318527B
Application number: CN201510347774.6A
Authority: CN
Inventors: 苏朔; 龙军; 段庆华; 武志强; 周涵; 赵毅; 赵晓光
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-06-19
Filing date: 2015-06-19
Publication date: 2019-05-17
Anticipated expiration: 2035-06-19
Also published as: CN106318527A

Abstract

The present invention relates to a kind of methanol-fueled engine lubricant oil composites, including shielding phenolic compounds ashless dispersant, metal detergent, ZDDP, organic-molybdenum and major amount of lubricating base oil；The structure of the shielding phenolic compounds is shown in formula (I):

Description

Methanol-fueled engine lubricant oil composite and its manufacturing method

Technical field

The present invention relates to a kind of methanol-fueled engine lubricant oil composites.Specifically, the present invention relates to one kind to have The methanol fuel that superior oxidation resistance energy, detergent-dispersant performance energy, abrasion resistance, rustless property and control acid value increase performance starts Engine oil base oil.

Background technique

Currently, widely used zinc dialkyl dithiophosphate (ZDDP) is a kind of multiple-effect antioxygen antiwear additive in lubricating oil, There are antioxidant effect outstanding and outstanding abrasion resistance.However, P elements can make the catalyst in Exhaust Gas Catalytic Converter for Automobiles Poison deactivation, it is very unfavorable to protection environment.With the increasingly raising of environmental requirement, lubricating oil is intended to low-phosphorous low ash, very To being without phosphorus no ashing.This makes the usage amount of ZDDP severely limited, and the oxidation stability and abrasion resistance of oil product obtain not To fully ensuring that.

Though methanol fuel is a kind of novel alternative energy source with wide application prospect, the by-product that methanol burning generates Acidity is strong, it is rotten to easily lead to engine oil.Methanol gasoline in use, unavoidably has methanol to enter in lubricating oil.Hair Gas blowby in the motivation course of work, the cooling procedure of engine working process are likely to make methanol condensed and enter lubricating oil.First Alcohol can aoxidize generation formaldehyde in combustion, and then aoxidize and generate formic acid.Due to formic acid acidity it is higher, can in lubricating oil Alkaline detersive react.Therefore, requirement of the methanol gasoline engine than petrol engine to lubricating oil is higher, it is desirable that its With the requirement such as better antioxygenic property, piston detergency and superior wear resistance, this is also current technical research In difficult point.US 5304314 discloses a kind of phenolic compounds for being suitable as sulfur-bearing and arylamine that antioxidant uses.US 2006/0189824A1 discloses a kind of shielding phenolic compounds containing secondary aromatic amine for being suitable as antioxidant and using.But this The compound of a little prior arts is in methanol-fueled engine lubricating oil in use, the antioxygenic property of oil product, detergent-dispersant performance Room for improvement can be still remained with abrasion resistance.In addition, the corrosion of engine also can other than the adverse effect of deposit The service life of serious curtailment engine, and the corrosion of some key positions largely also influences the operating condition of engine Energy.The prior art is also far from enough to the concern of rustless property.

Therefore, a kind of methanol-fueled engine lubricant oil composite is still required in the prior art, is not only able to meet and work as The requirement increasingly harsh to antioxygenic property of modern more high standard product, and also show excellent detergent-dispersant performance energy, wear-resistant Performance and rustless property.

Summary of the invention

The present inventor passes through diligent research on the basis of existing technology, it was found that a kind of novel shielding phenolate conjunction Object, and it has furthermore been found that by using the shielding phenolic compounds as antioxidant, so that it may it solves of the existing technology aforementioned Problem, and have thus completed the present invention.

Specifically, the present invention relates to the contents of following aspect.

1. a kind of methanol-fueled engine lubricant oil composite, comprising shielding phenol, ashless dispersant, metal detergent, ZDDP, organic-molybdenum and major amount of lubricating base oil, the shielding phenol is as shown in logical formula (I):

In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C_1-300Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II) Group shown in group and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；Each group R' is each other It is identical or different, it is each independently selected from hydrogen and C_1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C_1-4Straight chain Or branched alkyl),

In aforementioned each logical formula (II), (III) and (IV), group L, which is selected from, is optionally selected from C by one or more_1-20Alkyl is (excellent Select C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group) and C_3-20What the substituent group of linear chain or branched chain miscellaneous alkyl replaced M+1 valence C_2-20Linear or branched alkyl group and optionally by one or more be selected from C_1-20Alkyl (preferably C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group) and C_3-20The m+1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces_3-20Linear chain or branched chain is miscellaneous Alkyl；Group L' is groupWherein group R " is selected from hydrogen, C_1-20Alkyl (preferably C_1-20Linear chain or branched chain alkane Base) and C_3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from hydrogen, C_1-10Linear or branched alkyl group and C_3-10Linear chain or branched chain miscellaneous alkyl； Each group A is same or different to each other, and is each independently selected from(wherein, Each group R is same or different to each other, and is each independently selected from hydrogen, C_1-300Linear or branched alkyl group (preferably C_1-10Linear chain or branched chain Alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), shown in group and logical formula (III) shown in logical formula (II) Group (is preferably each independently selected from hydrogen and C_1-300Linear or branched alkyl group)；Each group R' is same or different to each other, respectively solely On the spot it is selected from hydrogen and C_1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C_1-4Linear or branched alkyl group)；Two A group R and group-S- occupies three positions of the residue on phenyl ring respectively), on condition that at least one group A isM is 1 to 4 integer (preferably 1)；Each group R₂Phase each other It is same or different, it is each independently selected from hydrogen, C_1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V) Group (be preferably each independently selected from hydrogen, C_1-10Group shown in linear or branched alkyl group and logical formula (IV))；Each group R_bThat This is identical or different, is each independently selected from hydrogen and C_1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C_1-10Directly Chain or branched alkyl)；Each group R_cIt is same or different to each other, is each independently selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20 Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group Oxygroup is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；Z is 0 To 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n is 1 to 8；The integer (preferably 0,1 or 2) that n' is 0 to 7, on condition that N'+n≤8 (preferably n'+n=1 or n'+n=2)；Each group R_dIt is same or different to each other, is each independently selected from hydrogen and general formula (V) group shown in (preferably hydrogen)；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and Naphthalene nucleus (preferably phenyl ring), wherein two adjacent cyclic groupsOptionally pass through additional S atom each other and bridges this The N atom of two rings and form phenthazine ring, and/or, two adjacent cyclic groupsEach other optionally by additional Group(wherein group R " is selected from hydrogen, C_1-20Alkyl (preferably C_1-20Linear or branched alkyl group) and C_3-20Directly Chain or branched heteroalkyl groups, are preferably selected from hydrogen and C_1-10Linear or branched alkyl group) and bridge the N atom of the two rings and form 9, 10- acridan ring,

In logical formula (V), each group A is same or different to each other, and is each independently selected from Wherein each group R is same or different to each other, and is each independently selected from hydrogen, C_1-300Directly Chain or branched alkyl (preferably C_1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), general formula (II) group shown in group shown in and logical formula (III) (is preferably each independently selected from hydrogen and C_1-300Linear chain or branched chain alkane Base)；Each group R' is same or different to each other, and is each independently selected from hydrogen and C_1-20Linear or branched alkyl group is (preferably respectively independent Ground is selected from hydrogen and C_1-4Linear or branched alkyl group)；A two group R and group-S- occupy three positions of the residue on phenyl ring respectively It sets；Group L, group R₂, group R_b, group R_c, group R_d, cyclic groupAnd y, n, z and m are respectively provided with and lead to Identical meaning in formula (II),

Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH₂Being selected from-O- ,-S- and-NR'-, (R' is H or C_1-4Straight chain Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition, The wherein shielding phenolic compounds at least one group R in its entire molecular structure_dIt is hydrogen.

2. according to shielding phenolic compounds described in any preceding aspect, particular compound selected from the following or its arbitrary proportion Mixture:

3. a kind of methanol-fueled engine lubricant oil composite, comprising shielding phenol, ashless dispersant, metal detergent, ZDDP, organic-molybdenum and major amount of lubricating base oil, the manufacturing method of the shielding phenolic compounds include making shown in logical formula (X) It reacts in the presence of amine compounds multi-halogenated compounds shown in general formula (A) shown in phenolic compounds and general formula (Y) First step, optionally further include make the reaction product of the first step reacted with vulcanizing agent (preferably sulphur) and/or with general formula (Z) Shown in aldehyde compound (preferably formaldehyde) reaction additional step,

In logical formula (X), each group R₀It is same or different to each other, is each independently selected from hydrogen ,-SH and C_1-300Linear chain or branched chain Alkyl (preferably C_1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), on condition that at least one A group R₀It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C_1-20Linear or branched alkyl group is (preferably It is each independently selected from hydrogen and C_1-4Linear or branched alkyl group),

In general formula (Y), group R'₂Selected from hydrogen, C_1-20Linear or branched alkyl group and groupEach base Group R_bIt is same or different to each other, is each independently selected from hydrogen and C_1-20Linear or branched alkyl group (be preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group)；Each group R_cIt is same or different to each other, is each independently selected from hydrogen, C_1-20Linear or branched alkyl group And C_1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Straight chain or branch Alkyl group oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n1 is 1 to 8；Each cyclic groupPhase each other It is same or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),

In general formula (A), group R_haloSelected from optionally by one or more selected from C_1-20Alkyl (preferably C_1-20Linear chain or branched chain Alkyl, C_6-20Aryl or combinations thereof group) and C_3-20The m1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces_2-20Straight chain or branch Alkyl group and optionally by one or more be selected from C_1-20Alkyl (preferably C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof base Group) and C_3-20The m1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces_3-20Linear chain or branched chain miscellaneous alkyl, group Halo are halogen Element, the integer (preferably 2) that m1 is 2 to 5,

In general formula (Z), group R " is selected from hydrogen, C_1-20Alkyl (preferably C_1-20Linear or branched alkyl group) and C_3-20Straight chain or branch Chain miscellaneous alkyl is preferably selected from hydrogen, C_1-10Linear or branched alkyl group and C_3-10Linear chain or branched chain miscellaneous alkyl,

Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH₂Being selected from-O- ,-S- and-NR'-, (R' is H or C_1-4Straight chain Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition.

4. according to manufacturing method described in any preceding aspect, wherein in the first step, shown in the logical formula (X) Phenolic compounds and the general formula (Y) shown in amine compounds molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably The molar ratio of 1:0.8-2.0, phenolic compounds and multi-halogenated compounds shown in the general formula (A) shown in the logical formula (X) is 1:0.1-10, preferably 1:0.2-5.0, more preferable 1:0.3-3.0, in the additional step, amination shown in the general formula (Y) The molar ratio for closing object and the vulcanizing agent is 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-3.0, general formula (Y) institute The molar ratio of aldehyde compound shown in the amine compounds that show and the general formula (Z) is 1:0.1-10, preferably 1:0.5-5.0, more excellent Select 1:0.8-2.0.

5. in the methanol-fueled engine lubricant oil composite described in any preceding aspect, the shielding phenolic compounds is accounted for The 0.001%-30% of the methanol-fueled engine lubricant oil composite total weight, preferably 0.05%-20%, more preferably 0.1%-10%；

The ashless dispersant can select polyisobutene succinimide；The polyisobutene succinimide can select With monosubstituted polyisobutene succinimide, disubstituted polyisobutene succinimide, polysubstituted polyisobutene succinimide With one of boronation polyisobutene succinimide or a variety of, wherein the number-average molecular weight of the part polyisobutene (PIB) is 800-4000, preferably 900-3000, preferably 1000-2400, for example, can select Suzhou specialty oil factory produce T151, T161, T161A, T161B of the production of Jinzhou Petrochemical Company additive factory, the production of Lu Borun Lan Lian additive Co., Ltd LZLl57, LZ6418, LZ6420 of Lubrizol Corp.'s production, the Hitec646 etc. of Afton Chemical Corp.'s production；The dispersing agent is excellent Choosing is selected from disubstituted polyisobutene succinimide and/or boronation polyisobutene succinimide；The dispersing agent accounts for the first The 0.5%-15% of alcohol engine lubricant oil composite gross mass, preferably 1%-10%, more preferable 1.5%-8%；

The metal detergent can select sulfonate and/or alkyl monosulfide phenates；The sulfonate can select sulfonic acid One of calcium, sulfonic acid magnesium, barium sulfonate and sodium sulfonate are a variety of, the alkyl monosulfide phenates can select sulfurized alkylphenol calcium, One or both of sulfenyl phenolate magnesium；The metal detergent is preferably selected from the sulfurized alkylphenol calcium, most preferably base number The combination of SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and middle base number sulfurized alkylphenol calcium；The sulfonic acid magnesium and the sulfurized alkylphenol calcium, can With LZL115A, the LZL115B for selecting Lu Borun Lan Lian additive Co., Ltd to produce, Lubrizol Corporation production LZ6499, LZ6500, Afton Corporation production Hitec7637, Chevron Oronite Company production OLOA219, the C9340 etc. of Infineum company production；The metal detergent accounts for the methanol-fueled engine lubricating oil The 0.2%-20% of composition gross mass, preferably 0.8%-15%, more preferable 1.2%-10%；

The ZDDP can select C_2-12Alkyl ZDDP, is preferably selected from C_3-8Alkyl ZDDP, alkyl can select ethyl, N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethyl One of hexyl, cyclohexyl and methylcyclopentyl are a variety of；The ZDDP can select Wuxi south petroleum additive limited T202, T203 of company's production, primary alkyl T202, the primary alkyl T203, brothers alkane of the production of Jinzhou Petrochemical Company additive factory Base T204, secondary alkyl T205, LZ1371, LZ1375 of the production of company, Lubrizol Corp., the C9417 of Run Yinglian company production, C9425, C9426, Hitec7169, Hitec1656 etc. of Afton Chemical Corp.'s production；The ZDDP accounts for the methanol fuel and starts The 0.1%-10% of machine lubricant oil composite gross mass, preferably 0.2%-8%, more preferable 0.5%-5%；

The organic-molybdenum is selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, dialkyl dithio ammonia One of base formic acid molybdenum, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdates esters are more Kind, have the organic group comprising enough carbon atom numbers so that organic-molybdenum chemical combination _ object dissolves in these organic molybdenums Or be scattered in lubricating base oil, the general carbon atom number is between 6-60, between preferably 10-50；The organic-molybdenum can With selected from the U.S. Vanderbilt company production MolyVan L, 822,855, the Japanese rising sun electrification company production 515,525, 710；The organic-molybdenum is preferably selected from molybdenum dialkyldithiocarbamacompositions；The organic-molybdenum accounts for the methanol-fueled engine profit The 0.01%-10% of sliding oil composition gross mass, preferably 0.05%-5%, more preferable 0.1%-2%.

The lubricating base oil can select one of API I, II, III, IV and V class lubricating base oil or a variety of, For example it can enumerate selected from one of mineral lubricating oil and synthetic lubricant fluid or a variety of；The viscosity index (VI) of the lubricating base oil Generally higher than 80, saturated hydrocarbon content mass fraction is greater than 90% and sulfur content mass fraction is less than 0.03%.

Antioxidant can also be added in methanol-fueled engine lubricant oil composite of the invention, Ashless friction improves One of agent, pour-point depressant, viscosity index improver, metal corrosion inhibitor, antirust agent and anti-foaming agent or various other lubrications Oil additive.These additives can be used alone, and can also be used with combination of two or more, and its dosage is from this field Conventional amount used is not particularly limited.

It is by by the shielding phenol 6. according to methanol-fueled engine lubricant oil composite described in any preceding aspect Compound, ashless dispersant, metal detergent, ZDDP, organic-molybdenum are mixed with the lubricating base oil and are manufactured.

Technical effect

Shielding phenolic compounds according to the present invention, phosphorus element-containing and metallic element, are not likely to produce ash content, are environmental-friendly The antioxidant of type.

Shielding phenolic compounds according to the present invention shows the high temperature significantly improved compared with the compound of the prior art Antioxygenic property (thermal stability) can effectively improve (high temperature) oxidation stability of such as lubricating oil.

Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, excellent rustless property is also exhibited further.This is not available for prior art compound.

Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, excellent cleansing performance (i.e. deposit generation rejection) is also exhibited further.This is the prior art It closes not available for object.

Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment While performance, also exhibits further excellent inhibition viscosity build and inhibit the increased performance of acid value.This is the prior art Not available for compound.

Methanol-fueled engine lubricant oil composite of the invention have excellent antioxygenic property, detergent-dispersant performance energy, Abrasion resistance and rustless property sufficiently meet SM and the above specification engine for carbinol gasoline fuel such as M15, M85, M100 The requirement of oil product.

Specific embodiment

Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.

All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference. Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain Justice.In case of conflict, it is subject to the definition of this specification.

When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.

In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in Hold, unless those skilled in the art think that the combination is obvious unreasonable.

In the context of the present invention, statement " halogen " refers to fluorine, chlorine, bromine or iodine.

In the context of the present invention, term " alkyl " has conventionally known in the art meaning, including linear chain or branched chain Alkyl, linear chain or branched chain alkenyl, linear chain or branched chain alkynyl, naphthenic base, cycloalkenyl, cycloalkynyl radical, aryl or combinations thereof group, wherein It is preferred that linear or branched alkyl group, linear chain or branched chain alkenyl, aryl or combinations thereof group.It, specifically such as can be with as the alkyl Enumerate C_1-20Alkyl, including C_1-20Linear or branched alkyl group, C_2-20Linear chain or branched chain alkenyl, C_2-20Linear chain or branched chain alkynyl, C_3-20 Naphthenic base, C_3-20Cycloalkenyl, C_3-20Cycloalkynyl radical, C_6-20Aryl or combinations thereof group, wherein it is preferred that C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group.As the combination group, for example one or more C can be enumerated_1-20Linear or branched alkyl group (preferably one or more C_1-10Linear or branched alkyl group) and one or more C_6-20Aryl (preferably one or more phenyl or naphthalene Base) group that is obtained by Direct Bonding.As the combination group, for example it can further enumerate one or more C_1-10Straight chain Or branched alkyl phenyl, phenyl C_1-10Linear or branched alkyl group or one or more C_1-10Linear or branched alkyl group phenyl C_1-10Straight chain Or branched alkyl etc., wherein more preferable C_1-10Linear or branched alkyl group phenyl (such as tert-butyl-phenyl), phenyl C_1-10Straight chain or branch Alkyl group (such as benzyl) or C_1-10Linear or branched alkyl group phenyl C_1-10Linear or branched alkyl group (such as t-butylbenzyl).

In the context of the present invention, so-called " linear chain or branched chain miscellaneous alkyl ", refers to linear or branched alkyl group molecule knot Inside structure (not including the end of main chain or any side chain in the alkyl molecule structure) one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH₂Being selected from-O- ,-S- and-NR'-, (R' is H or C_1-4One of linear or branched alkyl group) Substituting group directly substitute and (do not include the alkyl point inside the group that obtains or linear or branched alkyl group molecular structure The end of main chain or any side chain in minor structure) one or more (such as 1 to 3,1 to 2 or 1) group-CH < quilt Substituting group-N < directly is substituted and the group that obtains.As the substituting group, preferably-O- or-S-, more preferable-S-.Obviously , for the angle of structural stability, when there are multiple, not Direct Bonding between these substituting groups.Though in addition, The carbon atom number of the right linear or branched alkyl group is because of group-CH₂Or group-CH < accordingly reduced by substitution, but for table Simplicity is stated, still refers to the linear chain or branched chain miscellaneous alkyl with the carbon atom number of the substitution foregoing description linear or branched alkyl group Carbon atom number.As the linear chain or branched chain miscellaneous alkyl, for concrete example, C₄Straight chained alkyl is such as(group indicated by arrow is not in inside molecular structure in formula, but is located In the end of main chain) it is directly substituted by a substituting group-O- by acquisition-CH₂-O——CH₂-CH₃Or Inside molecular structure, but it is in the end of main chain and side chain) it will be obtained by a substituting group-N < directly substitutionReferred to as C₄Branched heteroalkyl groups.According to the present invention, as the miscellaneous alkane of the linear chain or branched chain Base, for example C can be enumerated_3-20Linear chain or branched chain miscellaneous alkyl, wherein it is preferred that C_3-10Linear chain or branched chain miscellaneous alkyl or C_3-6Straight chain or Branched heteroalkyl groups.

In the context of the present specification, expression way " number+valence+group " or its refer to similar to term from the group It removes in corresponding foundation structure (such as chain, ring or combinations thereof etc.) and obtains after the hydrogen atom of quantity representated by the number Group preferably refers to remove on the carbon atom (preferably saturated carbon atom and/or the non-same carbon atom) contained by the structure The group obtained after the hydrogen atom of quantity representated by the number.For example, " trivalent linear or branched alkyl group " is referred to from straight The group for removing 3 hydrogen atoms on chain or branched paraffin (i.e. basic chain corresponding to the linear or branched alkyl group) and obtaining, and " divalent linear chain or branched chain miscellaneous alkyl " then refer to from the miscellaneous alkane of linear chain or branched chain (the preferably carbon atom contained by the miscellaneous alkane, or Person is further, from the non-same carbon atom) on remove 2 hydrogen atoms and the group that obtains.

In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.

In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration Chromatography (GPC) measurement.

In the context of the present specification, in case of no particular description, any gel permeation chromatography being related to (GPC) or the determination condition of GPC spectrogram is equal are as follows: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis Instrument；Mobile phase uses tetrahydrofuran, flow velocity 1mL/min, and chromatogram column temperature is 35 DEG C, delivery time 40min, sample quality point Number is 0.16%-0.20%.

According to the present invention, it is related to shielding phenolic compounds shown in a kind of logical formula (I).

According to the present invention, in logical formula (I), when there are multiple, each group R is same or different to each other, each independently Selected from hydrogen, C_1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III), on condition that at least One group R is group shown in logical formula (II).

According to the present invention, in logical formula (I), as the C_1-300Linear or branched alkyl group, for example C can be enumerated_1-20Directly Chain or branched alkyl (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4Linear or branched alkyl group) or it is polyolefin-based.As Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly- The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.

According to embodiment of the present invention, in logical formula (I), there are multiple group R, one of group R is logical Group shown in formula (II), one in other two group R be it is described polyolefin-based, the other is hydrogen, C_1-20Straight chain or branch Alkyl group (preferably C_1-10Linear or branched alkyl group) or logical formula (III) shown in group.

According to embodiment of the present invention, in logical formula (I), when group R is described polyolefin-based, the polyolefin Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (I).

According to the present invention, in logical formula (I), when there are multiple, each group R' is same or different to each other, each independently Selected from hydrogen and C_1-20Linear or branched alkyl group.

According to embodiment of the present invention, in logical formula (I), when there are multiple, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C_1-4Linear or branched alkyl group.

According to the present invention, in logical formula (II), group L is selected from the m+1 valence C optionally replaced_2-20Linear or branched alkyl group and The m+1 valence C optionally replaced_3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from the m+1 valence C optionally replaced_2-10Linear or branched alkyl group The m+1 valence C optionally replaced_3-10Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m+1 valence C optionally replaced_2-6Linear chain or branched chain Alkyl and the m+1 valence C optionally replaced_3-6Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m+1 valence C optionally replaced_2-6Straight chain or branch Alkyl group.

According to the present invention, in logical formula (II), in the definition of group L, so-called optional substitution is referred to optionally by one Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) are selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl takes Replace for base.As the substituent group, preferably C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group.As described C_1-20Linear or branched alkyl group, preferably C_1-10Linear or branched alkyl group, more preferable C_1-6Linear or branched alkyl group, for example, methyl or Ethyl.

According to the present invention, in logical formula (II), m is 1 to 4 integer, preferably 1.

According to the present invention, in logical formula (II), each group A is same or different to each other, and is each independently selected from following general formula (II-1) group shown in group and following general formula shown in (II-2), on condition that at least one group A is following general formula (II- 1) group shown in.

According to the present invention, in general formula (II-1), group R₂Selected from hydrogen, C_1-20Shown in linear or branched alkyl group, logical formula (IV) Group and logical formula (V) shown in group.

According to embodiment of the present invention, in general formula (II-1), group R₂Selected from hydrogen, C_1-10Linear chain or branched chain alkane Group shown in base and logical formula (IV).

According to the present invention, in general formula (II-1), when there are multiple, each group R_bIt is same or different to each other, respectively solely On the spot it is selected from hydrogen and C_1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (II-1), when there are multiple, each group R_bIt is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-6Linear or branched alkyl group, preferably hydrogen.

According to the present invention, in general formula (II-1), when there are multiple, each group R_cIt is same or different to each other, respectively solely On the spot it is selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (II-1), when there are multiple, each group R_cIt is mutually the same Or it is different, it is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (II-1), a preferably group R_cIn cyclic groupUpper N atom is (that is, with group R_dThe N atom of bonding) contraposition.

According to the present invention, in general formula (II-1), y is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (II-1), z is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (II-1), the integer that n is 1 to 8, preferably 1 or 2.

According to the present invention, in general formula (II-1), when there are multiple, each group R_dIt is same or different to each other, respectively solely On the spot it is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).

According to the present invention, in general formula (II-1), when there are multiple, each cyclic group(in general formula (II- 1) inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably at general formula (II-1) Inside configuration be rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as 1,4- or 2,6- in the inside configuration of general formula (II-1) Naphthylene), wherein it is preferred that phenyl ring.

According to embodiment of the present invention, in general formula (II-1), two adjacent cyclic groupsThat This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group R_dThe N of bonding Atom) and form phenthazine ring, i.e.,

Embodiment according to the present invention, in general formula (II-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed, It is not necessary to require these cyclic groupsEach of with another adjacent cyclic group Form the phenthazine ring.

According to embodiment of the present invention, in general formula (II-1), two adjacent cyclic groupsThat This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with Group R_dThe N atom of bonding) and form 9,10- acridan ring, i.e.,

According to the present invention, in groupIn, group R " is selected from hydrogen, C_1-20Alkyl (preferably C_1-20Straight chain or Branched alkyl) and C_3-20Linear chain or branched chain miscellaneous alkyl.

According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C_1-10Straight chain Or branched alkyl.

Embodiment according to the present invention, in general formula (II-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.

According to the present invention, in general formula (II-2), when there are multiple, each group R is same or different to each other, respectively independent Ground is selected from hydrogen, C_1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).

According to the present invention, in general formula (II-2), two group R and a group-S- occupy the residue on phenyl ring respectively Three positions.

According to embodiment of the present invention, in general formula (II-2), when there are multiple, each group R is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-300Linear or branched alkyl group.

According to the present invention, in general formula (II-2), as the C_1-300Linear or branched alkyl group, for example C can be enumerated_1-20 Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4Linear or branched alkyl group) or it is polyolefin-based.Make To be described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described Polyolefin-based number-average molecular weight Mn, preferably 500-2000, more preferable 500-1500.According to the present invention, the polyolefin-based (base In sheet) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyene of the polyolefin as starting material The difference of hydrocarbon manufacturing method, may also be containing a small amount of olefinic double bond (such as in polyolefin system in the polyolefin-based strand Remain or introduce during making), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.

According to embodiment of the present invention, in general formula (II-2), there are multiple group R, one of group R is It is described polyolefin-based, the other is hydrogen or C_1-20Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4 Linear or branched alkyl group).

According to embodiment of the present invention, in general formula (II-2), when group R is described polyolefin-based, this is poly- Alkylene is preferably placed at the contraposition of phenolic hydroxyl group in general formula (II-2).

According to the present invention, in general formula (II-2), when there are multiple, each group R' is same or different to each other, respectively solely On the spot it is selected from hydrogen and C_1-20Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (II-2), when there are multiple, each group R' is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-4Linear or branched alkyl group.

According to the present invention, in logical formula (III), group L' is group

According to the present invention, in logical formula (III), in the definition of group L', group R " is selected from hydrogen, C_1-20Alkyl is (preferably C_1-20Linear or branched alkyl group) and C_3-20Linear chain or branched chain miscellaneous alkyl.

According to embodiment of the present invention, in logical formula (III), in the definition of group L', group R " be selected from hydrogen, C_1-10Linear or branched alkyl group and C_3-10Linear chain or branched chain miscellaneous alkyl, is preferably selected from hydrogen and C_1-10Linear or branched alkyl group.

According to the present invention, in logical formula (III), group R₂Selected from hydrogen, C_1-20Shown in linear or branched alkyl group, logical formula (IV) Group and logical formula (V) shown in group.

According to embodiment of the present invention, in logical formula (III), group R₂Selected from hydrogen, C_1-10Linear or branched alkyl group With group shown in logical formula (IV).

According to the present invention, in logical formula (III), when there are multiple, each group R_bIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C_1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group.

According to embodiment of the present invention, in logical formula (III), when there are multiple, each group R_bIt is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-6Linear or branched alkyl group, preferably hydrogen.

According to the present invention, in logical formula (III), when there are multiple, each group R_cIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in logical formula (III), when there are multiple, each group R_cIt is mutually the same Or it is different, it is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in logical formula (III), a preferably group R_cIn cyclic groupUpper N atom is (that is, with group R_dThe N atom of bonding) contraposition.

According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in logical formula (III), the integer that n is 1 to 8, preferably 1 or 2.

According to the present invention, in logical formula (III), when there are multiple, each group R_dIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).

According to the present invention, in logical formula (III), when there are multiple, each cyclic group(in logical formula (III) Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in logical formula (III) Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of logical formula (III) Base), wherein it is preferred that phenyl ring.

According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group R_dThe N of bonding Atom) and form phenthazine ring, i.e.,

Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed, It is not necessary to require these cyclic groupsEach of with another adjacent cyclic group Form the phenthazine ring.

According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with Group R_dThe N atom of bonding) and form 9,10- acridan ring, i.e.,

Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.

According to the present invention, in logical formula (IV), when there are multiple, each group R_bIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C_1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group.

According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group R_bIt is mutually the same or Difference is each independently selected from hydrogen and C_1-6Linear or branched alkyl group, preferably hydrogen.

According to the present invention, in logical formula (IV), when there are multiple, each group R_cIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group R_cIt is mutually the same or Difference is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in logical formula (IV), a preferably group R_cIn cyclic groupUpper N atom is (that is, with group R_dThe N atom of bonding) contraposition.

According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in logical formula (IV), the integer that n' is 0 to 7, preferably 0,1 or 2, on condition that n'+n≤8.According to An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical as the definition in aforementioned formula (II-1).

According to the present invention, in logical formula (IV), when there are multiple, each group R_dIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).

According to the present invention, in logical formula (IV), when there are multiple, each cyclic group(in logical formula (IV) Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV) Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (IV)), Wherein preferred phenyl ring.

According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group R_dThe N of bonding is former Son) and form phenthazine ring, i.e.,

Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine Ring.

According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base Group R_dThe N atom of bonding) and form 9,10- acridan ring, i.e.,

Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupIt is formed The acridan ring.

According to the present invention, in logical formula (V), group L is selected from the m+1 valence C optionally replaced_2-20Linear or branched alkyl group and appoint Choose the m+1 valence C in generation_3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from the m+1 valence C optionally replaced_2-10Linear or branched alkyl group and The m+1 valence C optionally replaced_3-10Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m+1 valence C optionally replaced_2-6Linear chain or branched chain alkane Base and the m+1 valence C optionally replaced_3-6Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m+1 valence C optionally replaced_2-6Linear chain or branched chain Alkyl.

According to the present invention, in logical formula (V), in the definition of group L, so-called optional substitution is referred to optionally by one Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) are selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl takes Replace for base.As the substituent group, preferably C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group.As described C_1-20Linear or branched alkyl group, preferably C_1-10Linear or branched alkyl group, more preferable C_1-6Linear or branched alkyl group, for example, methyl or Ethyl.

According to the present invention, in logical formula (V), m is 1 to 4 integer, preferably 1.

According to the present invention, in logical formula (V), each group A is same or different to each other, and is each independently selected from following general formula (V-1) group shown in group and following general formula shown in (V-2).

According to the present invention, in general formula (V-1), group R₂Selected from hydrogen, C_1-20Shown in linear or branched alkyl group, logical formula (IV) Group and logical formula (V) shown in group.

According to embodiment of the present invention, in general formula (V-1), group R₂Selected from hydrogen, C_1-10Linear or branched alkyl group With group shown in logical formula (IV).

According to the present invention, in general formula (V-1), when there are multiple, each group R_bIt is same or different to each other, it is respectively independent Ground is selected from hydrogen and C_1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (V-1), when there are multiple, each group R_bIt is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-6Linear or branched alkyl group, preferably hydrogen.

According to the present invention, in general formula (V-1), when there are multiple, each group R_cIt is same or different to each other, it is respectively independent Ground is selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (V-1), when there are multiple, each group R_cIt is mutually the same Or it is different, it is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (V-1), a preferably group R_cIn cyclic groupUpper N atom is (that is, with group R_dThe N atom of bonding) contraposition.

According to the present invention, in general formula (V-1), y is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (V-1), z is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (V-1), the integer that n is 1 to 8, preferably 1 or 2.

According to the present invention, in general formula (V-1), when there are multiple, each group R_dIt is same or different to each other, it is respectively independent Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).

According to the present invention, in general formula (V-1), when there are multiple, each cyclic group(at general formula (V-1) Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in general formula (V-1) Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of general formula (V-1) Base), wherein it is preferred that phenyl ring.

According to embodiment of the present invention, in general formula (V-1), two adjacent cyclic groupsThat This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group R_dThe N of bonding Atom) and form phenthazine ring, i.e.,

Embodiment according to the present invention, in general formula (V-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed, It is not necessary to require these cyclic groupsEach of with another adjacent cyclic group Form the phenthazine ring.

According to embodiment of the present invention, in general formula (V-1), two adjacent cyclic groupsThat This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with Group R_dThe N atom of bonding) and form 9,10- acridan ring, i.e.,

Embodiment according to the present invention, in general formula (V-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.

According to the present invention, in general formula (V-2), when there are multiple, each group R is same or different to each other, respectively independent Ground is selected from hydrogen, C_1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).

According to the present invention, in general formula (V-2), two group R and a group-S- occupy the residue three on phenyl ring respectively A position.

According to embodiment of the present invention, in general formula (V-2), when there are multiple, each group R it is mutually the same or Difference is each independently selected from hydrogen and C_1-300Linear or branched alkyl group.

According to the present invention, in general formula (V-2), as the C_1-300Linear or branched alkyl group, for example C can be enumerated_1-20 Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4Linear or branched alkyl group) or it is polyolefin-based.Make To be described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described Polyolefin-based number-average molecular weight Mn, preferably 500-2000, more preferable 500-1500.According to the present invention, the polyolefin-based (base In sheet) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyene of the polyolefin as starting material The difference of hydrocarbon manufacturing method, may also be containing a small amount of olefinic double bond (such as in polyolefin system in the polyolefin-based strand Remain or introduce during making), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.

According to embodiment of the present invention, in general formula (V-2), there are multiple group R, one of group R is It is described polyolefin-based, the other is hydrogen or C_1-20Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4 Linear or branched alkyl group).

According to embodiment of the present invention, in general formula (V-2), when group R is described polyolefin-based, the polyene Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in general formula (V-2).

According to the present invention, in general formula (V-2), when there are multiple, each group R' is same or different to each other, respectively independent Ground is selected from hydrogen and C_1-20Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (V-2), when there are multiple, each group R' is mutually the same Or it is different, it is each independently selected from hydrogen and C_1-4Linear or branched alkyl group.

According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula (II-2) or shown in general formula (V-2)), it is necessary to it include structureAs phenol unit.According to the present invention one it is preferred Embodiment, the shielding phenolic compounds is in its entire molecular structure comprising at most 5, at most 3, at most 2 or extremely More 1 phenol unit.

According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as general formula (II-1) or further such as Shown in logical formula (III), logical formula (IV) or general formula (V-1)), it is necessary to it include structureAs amine list Member.According to a preferred embodiment of the present invention, the shielding phenolic compounds includes at most 15 in its entire molecular structure A, at most 10, at most 8, at most 6, at most 4, at most 3 or at most 2 amine units.

According to the present invention, the shielding phenolic compounds preferably at least has (preferably 2,3 in its entire molecular structure It is a or 4 or more) group R_dIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure Have selected from least one of following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units, Cyclic groupIt is identical as the definition in general formula (II-1) with group R ".

A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely A few hydrogen amine unit (1).

Specifically, to shield phenolic compoundsFor, the compound is whole at its Include 2 phenol units and 2 amine units in a molecular structure, and includes 1 hydrogen amine unit (1).

According to the present invention, as the shielding phenolic compounds, for example following compound or its arbitrary proportion can be enumerated Mixture, but the present invention is not limited thereto.

According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can be with a kind of single shape of (pure) compound Formula exist, make or use, can also with the form of the mixture (in any proportion) of two or more of them exist, manufacture or It uses, this has no effect on the realization of effect of the present invention.

According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can pass through manufacturing method system below It makes, but is not limited thereto.

The manufacturing method according to the present invention, including make amination shown in phenolic compounds shown in logical formula (X) and general formula (Y) The first step to react in the presence of closing object multi-halogenated compounds shown in general formula (A).

According to the present invention, lead in formula (X), when there are multiple, each group R₀It is same or different to each other, selects each independently From hydrogen ,-SH and C_1-300Linear or branched alkyl group, on condition that at least one group R₀It is-SH.

According to the present invention, in logical formula (X), as the C_1-300Linear or branched alkyl group, for example C can be enumerated_1-20Directly Chain or branched alkyl (preferably C_1-10Linear or branched alkyl group, more preferable C_1-4Linear or branched alkyl group) or it is polyolefin-based.As Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly- The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright Really, and the present invention still polyolefin-based is classified as " alkyl " for this.

According to embodiment of the present invention, in logical formula (X), there are multiple group R₀, one of group R₀Be- SH, other two group R₀In one be it is described polyolefin-based, the other is hydrogen or C_1-20Linear or branched alkyl group is (preferably C_1-10Linear or branched alkyl group).

According to embodiment of the present invention, in logical formula (X), in group R₀When being described polyolefin-based, the polyene Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (X).

According to the present invention, in logical formula (X), when there are multiple, each group R' is same or different to each other, each independently Selected from hydrogen and C_1-20Linear or branched alkyl group.

According to embodiment of the present invention, in logical formula (X), when there are multiple, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C_1-4Linear or branched alkyl group.

According to the present invention, as phenolic compounds shown in the logical formula (X), commercially available product can be directly used, it can also To be manufactured by conventionally known in the art method, it is not particularly limited.In addition, as shown in the logical formula (X) Phenolic compounds, can be used only one kind, can also be used with combination of two or more.

According to the present invention, the manufacturing method as phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl In the presence of changing catalysts, make phenolic compounds shown in general formula (X') and polyolefin (number-average molecular weight Mn 300-3000, it is excellent Select 500-2000, more preferable 500-1500) occur alkylated reaction method.

According to the present invention, in general formula (X'), group R' has and identical meaning in aforementioned formula (X).

According to the present invention, there are three group R' in general formula (X')₀, one of group R'₀It is-SH, another group R'₀It is H, third group R'₀It is hydrogen ,-SH or C_1-20Linear or branched alkyl group (preferably C_1-10Linear or branched alkyl group).

According to embodiment of the present invention, in general formula (X'), at least one group R'₀It is H, and group R'₀ The contraposition of phenolic hydroxyl group in general formula (X').

According to the present invention, the polyolefin preferably passes through ethylene, propylene or C₄-C₁₀The homopolymerization of alpha-olefin passes through these Polyolefin obtained from two or more copolymerization in alkene.As the C₄-C₁₀Alpha-olefin, for example, can enumerate n-butene, Isobutene, n-pentene, n-hexylene, positive octene and positive decene.

According to the present invention, at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) in these polyolefin Polymer chain contains olefinic double bond at its end.The olefinic double bond is usually with the ethenylidene of high reaction activity or vinyl Existing for form.

According to the present invention, as the polyolefin, more preferable polybutene.Unless otherwise indicated, term as used herein " polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and by 1- butylene, 2- butylene and different Pass through polymer prepared by copolymerization two or three in butylene.It the commercial product of this quasi polymer may also be containing negligible Other olefinic components of amount, but this has no effect on implementation of the invention.

According to the present invention, as the polyolefin, further preferred polyisobutene (PIB), also referred to as high reaction activity are poly- Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) Belonging to double bond is provided by methyl ethenylidene.

As the catalyst for alkylation reaction, for example Lewis acid catalyst can be enumerated, for example, selected from alchlor, Boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network One of object or a variety of is closed, wherein it is preferred that boron trifluoride etherate and/or boron trifluoride methanol complex compound.These Catalyst for alkylation reaction can directly use commercially available product.

According to the present invention, in the alkylated reaction, phenolic compounds shown in the polyolefin, the general formula (X'), Molar ratio between the catalyst for alkylation reaction such as can be 1:1-3:0.1-0.5, preferably 1:1.5-3:0.1-0.4, Most preferably 1:1.5-3:0.2-0.4, but is not limited thereto.

According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, preferably 1h-8h, most preferably 3h- 5h, but is not limited thereto.

According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most It is preferred that 20 DEG C -100 DEG C, but is not limited thereto.

According to the present invention, the alkylated reaction can be in the presence of a solvent.As the solvent, such as can be with Enumerate C_6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably Use hexane.

According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute The phenolic compounds shown.

According to the present invention, in general formula (Y), group R'₂Selected from hydrogen, C_1-20Linear or branched alkyl group and group

According to the present invention, in general formula (Y), when there are multiple, each group R_bIt is same or different to each other, each independently Selected from hydrogen and C_1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C_1-10Linear or branched alkyl group.

According to embodiment of the present invention, in general formula (Y), when there are multiple, each group R_bIt is mutually the same or Difference is each independently selected from hydrogen and C_1-6Linear or branched alkyl group, preferably hydrogen.

According to the present invention, in general formula (Y), when there are multiple, each group R_cIt is same or different to each other, each independently Selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (Y), when there are multiple, each group R_cIt is mutually the same or Difference is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup.

According to embodiment of the present invention, in general formula (Y), a preferably group R_cIn cyclic groupUpper N atom is (that is, with group R_dThe N atom of bonding) contraposition.

According to the present invention, in general formula (Y), y is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (Y), z is 0 to 3 integer, preferably 0 or 1.

According to the present invention, in general formula (Y), the integer that n1 is 1 to 8, preferably 1 or 2.

According to the present invention, in general formula (Y), when there are multiple, each cyclic group(in the knot of general formula (Y) Bivalent group is rendered as inside structure) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of general formula (Y) Portion is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of general formula (Y)), wherein It is preferred that phenyl ring.

According to the present invention, as amine compounds shown in the general formula (Y), commercially available product can be directly used, not There is special limitation.In addition, one kind can be used only as amine compounds shown in the general formula (Y), it can also be two kinds or more Kind is applied in combination.

According to the present invention, in general formula (A), group R_haloSelected from the m1 valence C optionally replaced_2-20Linear or branched alkyl group and The m1 valence C optionally replaced_3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from the m1 valence C optionally replaced_2-10Linear or branched alkyl group and The m1 valence C optionally replaced_3-10Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m1 valence C optionally replaced_2-6Linear or branched alkyl group The m1 valence C optionally replaced_3-6Linear chain or branched chain miscellaneous alkyl is more preferably selected from the m1 valence C optionally replaced_2-6Linear chain or branched chain alkane Base.

According to the present invention, in general formula (A), in group R_haloDefinition in, so-called optional substitution refers to optionally by one A or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) is selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl Substituent group replaces.As the substituent group, preferably C_1-20Linear or branched alkyl group, C_6-20Aryl or combinations thereof group.As described C_1-20Linear or branched alkyl group, preferably C_1-10Linear or branched alkyl group, more preferable C_1-6Linear or branched alkyl group, for example, methyl or Ethyl.

According to the present invention, in general formula (A), group Halo is halogen, including fluorine, chlorine, bromine and iodine, wherein it is preferred that chlorine.

According to the present invention, in general formula (A), the integer that m1 is 2 to 5, preferably 2.

According to the present invention, as multi-halogenated compounds shown in the general formula (A), one kind can be used only, it can also two Kind or multiple combinations use.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula (X) molar ratio of phenolic compounds shown in and amine compounds shown in the general formula (Y) is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula (X) molar ratio of phenolic compounds shown in and multi-halogenated compounds shown in the general formula (A) is generally 1:0.1-10, preferably 1: 0.2-5.0, more preferable 1:0.3-3.0.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, the first step can depositing in solvent In lower progress.As the solvent, for example C can be enumerated_2-10Aliphatic nitrile (such as acetonitrile etc.), C_6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C_6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C_1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C_2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C_3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C_3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..As the solvent, preferably C_6-20Aromatic hydrocarbon (such as benzene, toluene, diformazan Benzene and isopropylbenzene), C_3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C_3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more With.

According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the first step, can be added without Catalyst can also be added in catalyst.As the catalyst, for example basic catalyst can be enumerated.It is urged as the alkalinity The salt of weak acid of agent, such as hydroxide such as sodium hydroxide and potassium hydroxide that alkali metal can be enumerated etc. or alkali metal Such as sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate and saleratus etc..These catalyst can be used only one Kind, it can also be used with combination of two or more.As the dosage of the catalyst, can directly be used referring to the conventional of the prior art Amount, is not particularly limited.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the first step There are special restriction, but generally 0.1h-48h, preferably 0.2-12h, most preferably 0.5-6h.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the first step There are special restriction, but generally 0-200 DEG C, preferably 20-180 DEG C, most preferably 60-120 DEG C.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the first step terminates, pass through Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step Reaction mixture) in remove the volatile materials such as solvent that may be present after, can be obtained the reaction product of first step.

According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the The additional step (hereinafter referred to as additional step A) that the reaction product of one step reacts with vulcanizing agent and (forms phenthazine ring).

According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the The reaction product of one step reacted with aldehyde compound shown in general formula (Z) (formed acridan ring) additional step (with It is known as additional step B down).

According to the present invention, in general formula (Z), group R " is selected from hydrogen, C_1-20Alkyl (preferably C_1-20Linear or branched alkyl group) and C_3-20Linear chain or branched chain miscellaneous alkyl.

According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C_1-10Linear or branched alkyl group And C_3-10Linear chain or branched chain miscellaneous alkyl.

According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C_1-10Linear chain or branched chain Alkyl.

According to the present invention, as aldehyde compound shown in the general formula (Z), for example C can be enumerated_1-6Aliphatic aldehyde and benzene Formaldehyde.

According to embodiment of the present invention, as the C_1-6Aliphatic aldehyde, for example C can be enumerated_1-6Straight chain or branch Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can be used its aqueous solution, Paraformaldehyde or paraformaldehyde form, are not particularly limited.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can be only carried out, The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both it is carrying out The additional step A carries out the additional step B again when, do not have to the precedence of the additional step A and the additional step B There is special restriction, can first carry out the additional step A, carries out the additional step again after additional step A terminates B, or the additional step B is first carried out, the additional step A is carried out again after additional step B terminates.In addition, each attached Product (that is, reaction product from previous additional step) separating step can be had by adding between step, can also be without product point From step, it is not particularly limited.

According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A It is carried out after the first step terminates.At this point, the reaction product of the first step is as previously described from described first It is separated in the reaction mixture of step.Alternatively, the reaction product of the first step can also be straight without the separation It connects in the form of the reaction mixture of the first step for carrying out the additional step A.Alternatively, the additional step A It can be carried out after the additional step B terminates.When the additional step A after the additional step B terminates when carrying out, The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.Or The reaction product of person, the additional step B can also directly be mixed without the separation with the reaction of the additional step B The form of object is for carrying out the additional step A.

According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, in the extra step In rapid A, as the vulcanizing agent, for example sulphur and sulfur dichloride can be enumerated etc., wherein it is preferred that sulphur.As the sulphur, such as can To enumerate sulphur or sublimed sulfur.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step A, the general formula (Y) molar ratio of amine compounds shown in and the vulcanizing agent is generally 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5- 3.0。

According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can depositing in solvent In lower progress.As the solvent, for example C can be enumerated_2-10Aliphatic nitrile (such as acetonitrile etc.), C_6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C_6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C_1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C_2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C_3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C_3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more With.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A is generally in catalyst In the presence of carry out.As the catalyst, for example the catalyst that the prior art uses for this purpose and routinely can be enumerated, specifically Such as iodine.As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step A There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step A There are special restriction, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step A terminates, lead to Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step A is obtained it is that may be present After the volatile materials such as solvent, the reaction product of additional step A can be obtained, or can also be without the separation, directly For subsequent reaction step (than additional step B as the aforementioned).

According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B It is carried out after the first step terminates.When the additional step B after the first step terminates when carrying out, described The reaction product of one step is separated from the reaction mixture of the first step as previously described.Alternatively, described The reaction product of one step can also be directly used in the form of the reaction mixture of the first step without the separation Carry out the additional step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When described For additional step B when carrying out after the additional step A terminates, the reaction product of the additional step A is as described herein It is separated from the reaction mixture of the additional step A.Alternatively, the reaction product of the additional step A can also be without The separation is crossed, and for carrying out the additional step B directly in the form of the reaction mixture of the additional step A.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, the general formula (Y) molar ratio of amine compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B can depositing in solvent In lower progress.As the solvent, for example C can be enumerated_2-10Aliphatic nitrile (such as acetonitrile etc.), C_6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C_6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C_1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C_2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C_3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C_3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more With.

According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the additional step B, can be not added Enter catalyst, catalyst can also be added.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..As the organic acid catalyst, than Methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.It, can be with as the dosage of the catalyst Directly referring to the conventional amount used of the prior art, it is not particularly limited.

According to the present invention, it is described shielding phenolic compounds manufacturing method in, the additional step B incipient stage or During person carries out, amine compounds shown in the general formula (Y) can also further be added as needed, thus forming 9, Group shown in aforementioned formula (III) is formed while 10- acridan ring.At this point, amine compounds shown in the general formula (Y) 1:0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8- are generally with the molar ratio of aldehyde compound shown in the general formula (Z) 2.0。

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step B There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step B There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.

According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step B terminates, lead to Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step B is obtained it is that may be present After the volatile materials such as solvent, the reaction product of additional step B can be obtained, or can also be without the separation, directly For subsequent reaction step (than additional step A as the aforementioned).

It is known in the art, aforementioned all reaction step (including the first step, the additional step A and The additional step B) generally carried out under the protection of inert gas atmosphere.As the inert gas, for example nitrogen can be enumerated Gas and argon gas etc., are not particularly limited.

According to the present invention, it is described shielding phenolic compounds manufacturing method in, as the first step reaction product, The reaction product of the reaction product of the additional step A or the additional step B can be a kind of single shielding phenolic compounds (for example shielding phenolic compounds shown in aforementioned formula (I)) is also possible to the mixture comprising a variety of shielding phenolic compounds.These Reaction product is all desired by the present invention, and the difference of existence form has no effect on the realization of effect of the present invention.Therefore, this theory These reaction products are collectively termed as to shielding phenolic compounds of the invention without distinction in bright book context.In consideration of it, according to The present invention, and be not present and these reaction products are further purified, or be further separated out a certain spy from these reaction products Determine the absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the further of desired effect of the present invention It is sometimes preferred for promotion, but for the present invention not necessarily.Even so, as the purifying or separation method, For example it can enumerate and the reaction product is purified or separated by the methods of column chromatography method or preparation chromatography.

According to embodiment of the present invention, the manufacturing method according to present invention shielding phenolic compounds above-mentioned is further related to The shielding phenolic compounds of manufacture.

According to embodiment of the present invention, it is related to a kind of methanol-fueled engine lubricant oil composite, it includes this Invent any shielding phenolic compounds (or mixture of its arbitrary proportion) above-mentioned, ashless dispersant, metal detergent, ZDDP, Organic-molybdenum and major amount of lubricating base oil.

Embodiment

The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.

Performance in embodiment and comparative example is evaluated as follows.

(1) high-temperature oxidation resistance is evaluated

The lubricant oil composite that embodiment or comparative example are manufactured is as test specimen, using Pressurized Differential scanning amount heat examination The antioxygenic property that (PDSC) evaluates the test specimen is tested, is indicated with the oxidation induction period (unit is min) of test specimen.PDSC The temperature of test is 210 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.

(2) deposit generates rejection evaluation

The hair of simulation piston deposit is carried out using the lubricant oil composite that embodiment or comparative example manufacture as test specimen Motivation crankcase coking simulation test.This method is that coking plate analog meter is added in 300ml test specimen, is heated to 150 DEG C, adopts The aluminium sheet spilled oil for being 310 DEG C to temperature with continuation mode weighs the burnt amount generated on aluminium sheet after 6 hours, (single with sediment yield Position is mg) it indicates, simulate the deposit on piston.Coking amount is higher, and the piston detergency for representing this test specimen is poorer.

(3) rustless property is evaluated

According to BRT ball rust test method, using the lubricant oil composite that embodiment or comparative example manufacture as test specimen, During entire bench test in 18 hours, the metal ball continuous contact acidic liquid and sky protected by the test specimen Gas measures metal spherical reflector intensity, gray scale test value is obtained, for evaluating corrosion degree after the end of the test.Acetic acid/hydrogen Bromic acid/hydrochloric acid/deionized water solution injection rate is 0.19 ml/hour, and air draught is 40 ml/mins, and oil temperature is 48℃.Corrosion degree is higher, shows that the rustless property of test specimen is poorer.

(4) inhibit viscosity build assessment of performance

The lubricant oil composite that embodiment or comparative example manufacture is subjected to IIIE simulation test (VIT) as test specimen. The experimental condition of this method is 180 DEG C, 72h, oxygen flow 5L/h, calculates the viscosity build rate (%) of test front and back sample.

(5) acid value is inhibited to increase assessment of performance

The lubricant oil composite that embodiment or comparative example manufacture is subjected to IIIE simulation test (VIT) as test specimen. The experimental condition of this method is 180 DEG C, 72h, oxygen flow 5L/h, calculates the acid value incrementss of test front and back sample (mgKOH·g^-1)。

Embodiment 1

In the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 58.79g is added Boron trifluoride ether (the alkylated reaction catalysis of (0.323mol) 2- tert-butyl -6- mercapto-phenol, 6.88g (0.048mol) Agent), polyisobutene (Mn=1000, the Jilin Chemical group fine chemicals of 100ml n-hexane solvent and 161.61g (0.162mol) Co., Ltd's manufacture), in 80 DEG C of reaction 2h.After reaction, reaction is cleaned using the potassium hydroxide solution that mass fraction is 5% Mixture is primary, and is washed to neutrality with hot water to remove catalyst, and then vacuum distillation removes solvent and unreacted phenol, obtains Obtain polyisobutene mercapto-phenol, hydroxyl value 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.

Example reaction equation is as follows:

From the nucleus magnetic hydrogen spectrum spectrum analysis of polyisobutene mercapto-phenol product: being polyisobutene at chemical shift 1.40 The characteristic peak of tert-butyl hydrogen on mercapto-phenol phenyl ring；It is unimodal for sulfydryl on polyisobutene mercapto-phenol phenyl ring at chemical shift 3.58 The characteristic peak of hydrogen；The unimodal characteristic peak for hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring at chemical shift 4.84；Chemical shift At 7.12 it is unimodal and 7.20 at it is unimodal be respectively polyisobutene mercapto-phenol phenyl ring on two hydrogen characteristic peak.By hydroxyl on phenyl ring The Definitions On Integration of hydrogen is 1, and the integral for obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, is approached Theoretical 1:1:1:1:1 is analyzed from nuclear magnetic spectrogram, has been synthesized the polyisobutene mercapto-phenol alkylation that expected contraposition replaces and has been produced Object.

Embodiment 2

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- methylphenols, 15.79 grams of-two chloro-2-methyls of (112mmol) Isosorbide-5-Nitrae are added Butane, 32.38 grams of (176mmol) 4-aminodiphenylamines, 3.45 grams of (25mmol) potassium carbonate and 100mL toluene stir rapidly, In 90 DEG C of reaction 1h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained by column chromatography for separation Final shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.00 (3H), 1.31 (1H), 1.40 (9H), 1.78 (1H), 1.98 (1H), 2.37 (3H), 2.99 (2H), 3.33 (2H), 4.83 (1H), 6.95-7.26 (12H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 20.4,21.2,30.1,33.7,34.5,43.8,114.3,118.9,119.4, 121.8,125.8,129.5,132.3,133.5,146.1,149.0,150.8；

C₂₈H₃₆N₂OS calculated value C 74.96, H 8.09, N 6.24, O 3.57, S 7.15；Measured value: C 74.88, H 8.13, N 6.21, O 3.54, S 7.09.

Embodiment 3

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 11.66 grams of (62mmol) Bromofumes, 28.15 grams (153mmol) 4-aminodiphenylamine, 0.79 gram of (7.5mmol) sodium carbonate and 100mL benzene stir rapidly, react at 25 DEG C 24h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation Cover phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 3.15 (2H), 3.63 (2H), 5.17 (1H), 5.32 (1H), 6.97-7.26 (11H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 29.6,32.7,34.6,47.5,114.3,118.9,119.4,121.8, 126.2,127.5,129.5,132.3,136.5,146.1,149.0,153.5；

C₂₈H₃₆N₂OS calculated value C 74.96, H 8.09, N 6.24, O 3.57, S 7.15；Measured value C 75.06, H 8.13, N 6.11, O 3.61, S 7.09.

Embodiment 4

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.15 grams of (15mmol) dichloroether, 10.14 grams (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, 0.55 gram of (5.1mmol) sodium carbonate and 100mL toluene stir rapidly, 90 DEG C reaction 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained finally by column chromatography for separation Shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 2.98 (2H), 3.34 (2H), 3.63 (2H), 3.76 (2H), 5.32 (1H), 6.80-7.27 (16H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 29.6,32.1,34.6,46.9,69.4,69.6,114.0,116.6,117.1, 119.3,121.8,126.2,129.2,136.5,142.8,146.1,148.7,153.5；

C₃₆H₄₄N₂O₂S calculated value C 76.02, H 7.80, N 4.92, O 5.63, S 5.64；Measured value C 76.09, H 7.85, N 4.83, O 5.65, S 5.60.

Embodiment 5

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 12.99 grams of (115mmol) 1,3- dichloropropanes, 18.49 Gram (69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine, 0.76 gram of (7.2mmol) sodium carbonate and 150mL benzene, Stirring rapidly, in 85 DEG C of reaction 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column layer Analyse isolated final shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.80 (6H), 1.11-1.21 (5H), 1.36 (18H), 1.67 (1H), 2.16- 3.47 (6H), 5.32 (1H), 6.80-7.17 (7H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 22.4,24.6,34.6,45.2,52.7,58.6,115.4,116.6,119.4, 121.8,126.2,129.5,136.6,144.1,153.5；C₃₅H₅₀N₂OS calculated value: C 76.87, H 9.22, N 5.12, O 2.93, S 5.86；Measured value: C 76.95, H 9.28, N 5.08, O 2.87, S 5.80.

Embodiment 6

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 3.57 grams of (15mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 20.81 grams of (103mmol) 1,3- dibromopropanes, 21.76 Gram (103mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine, 0.29 gram of (2.1mmol) sodium carbonate and 150mL benzene stirs rapidly, in 110 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, and Final shielding phenol product is obtained by column chromatography for separation.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 1.94 (2H), 2.95 (2H), 3.43 (2H), 5.32 (1H), 6.80-7.17 (16H), 7.20 (1H), 7.26 (4H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 28.5,29.6,29.9,34.6,47.2,114.0,116.6,117.7, 118.4,121.8,126.2,129.2,132.3,136.5,142.8,146.1,148.7,153.5；

C₄₁H₄₇N₃OS calculated value C 78.18, H 7.52, N 6.67, O 2.54, S 5.09；Measured value C 78.29, H 7.57, N 6.55, O 2.51, S 5.10.

Embodiment 7

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 34.51 grams of (145mmol) 2,6- di-t-butyl -4- mercapto-phenols, 5.95 grams of (35mmol) 2- chloroethyl -3- chloropropyl first are added Amine, 4.49 grams of (21mmol) 4- amino -4'- methoxy diphenylamines, 0.28 gram of (2.6mmol) sodium carbonate and 150mL benzene, are stirred rapidly It mixes, in 90 DEG C of reaction 2h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column chromatography for separation Obtain final shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 2.27 (3H), 2.65 (2H), 2.99 (2H), 3.09 (2H), 3.46 (2H), 3.76 (3H), 4.10 (1H), 5.32 (1H), 6.97-7.17 (10H), 7.20 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 29.6,34.5,35.1,40.6,45.2,53.4,54.3,55.5,114.3, 118.9,120.1,126.2,132.3,136.5,149.0,153.4,154.5；

C₃₂H₄₅N₃O₂S calculated value C 71.73, H 8.47, N 7.84, O 5.97, S 5.98；Measured value C 71.69, H 8.43, N 7.91, O 5.92, S 5.95.

Embodiment 8

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.07 grams of (9.51mmol) 1,3- dichloropropanes, 6.51 Gram (25mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, 0.65 gram of (6.5mmol) saleratus and 150mL benzene stir rapidly, 70 DEG C of reaction 6h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained most by column chromatography for separation Whole shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 2.26 (2H), 3.05 (2H), 3.48 (2H), 5.32 (1H), 6.80-7.17 (12H), 7.27 (2H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 28.5,29.6,33.4,34.6,44.2,81.5,114.0,117.1,119.4, 121.8,126.2,129.5,136.6,142.8,146.1,148.7,153.4；

C₃₅H₄₂N₂OS calculated value C 78.02, H 7.86, N 5.20, O 2.97, S 5.95；Measured value: C 78.09, H 7.91, N 5.15, O 2.93, S 5.87.

Embodiment 9

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 8.33 grams of (35mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.30 grams of (51mmol) 1,3- dibromopropanes, 9.61 grams (31mmol) N, N'- diphenyl -2,6- naphthylenediamine, 0.24 gram of (1.71mmol) potassium carbonate and 150mL toluene stir rapidly, 110 DEG C of reaction 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained by column chromatography for separation Final shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 1.99 (2H), 3.06 (2H), 3.52 (2H), 5.32 (1H), 5.80 (1H), 6.99-7.27 (15H), 7.40 (1H), 7.84 (2H)；

¹³C NMR (75MHz, CDCl₃): δ 28.5,29.6,29.9,34.6,43.0,106.9,111.1,114.0, 116.5,119.9,121.4,126.2,128.9,129.1,129.4,136.5,140.7,142.8,147.5,148.7, 153.5；

C₃₉H₄₄N₂OS calculated value C 79.55, H 7.53, N 4.76, O 2.72, S 5.45；Measured value C 79.49, H 7.51, N 4.79, O 2.70, S 5.41.

Embodiment 10

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 6.19 grams of (26mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 13.16 grams of (92mmol) dichloroether, 3.84 grams (17mmol) N- isopropyl-N'- diphenyl-para-phenylene diamine, 0.43 gram of (3.1mmol) potassium carbonate and 150mL ethyl alcohol stir rapidly, 80 DEG C of reaction 2h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained most by column chromatography for separation Whole shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.19 (6H), 1.36 (18H), 3.04 (2H), 3.25 (2H), 3.35 (2H), 3.43 (1H), 3.49 (2H), 5.32 (1H), 6.80-7.26 (11H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 19.9,29.6,31.9,34.6,44.5,54.3,69.24,116.6,117.2, 119.3,121.8,126.2,129.5,136.5,142.8,146.1,153.4,154.8；

C₃₃H₄₆N₂O₂S calculated value C 74.11, H 8.67, N 5.24, O 5.98, S 6.00；Measured value C 74.05, H 8.61, N 5.29, O 5.93, S 6.07.

Embodiment 11

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.56 grams of (31mmol) 1,6- dibromo-hexanes, 5.70 grams (31mmol) 4-aminodiphenylamine, 0.12 gram of (0.85mmol) potassium carbonate and 150mL ethyl alcohol stir rapidly, react at 60 DEG C After 2.5h, it is down to room temperature, 7.05 grams of (85mmol) formaldehyde are added, are warming up to 85 DEG C of reaction 2.5h.To which after reaction, decompression is steamed A small amount of water of solvent and generation is removed in distillation, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.32 (2H), 1.36 (18H), 1.41 (2H), 1.64-1.81 (4H), 2.93- 3.28 (4H), 4.14 (2H), 4.43 (1H), 4.59 (1H), 5.32 (1H), 6.82-7.21 (9H)；

¹³C NMR (75MHz, CDCl₃): δ 26.8,28.3,28.6,29.6,31.8,33.1,34.3,44.56,113.0, 118.9,119.6,122.4,123.3,125.1,126.4,127.9,132.2,140.5,148.5,153.4；

C₃₃H₄₄N₂OS calculated value C 76.70, H 8.58, N 5.42, O 3.10, S 6.20；Measured value C 76.69, H 8.51, N 5.49, O 3.12, S 6.18.

Embodiment 12

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols, 39.20 grams of iodo- 2- methyl fourths of (121mmol) Isosorbide-5-Nitrae-two are added Alkane, 19.93 grams of (94mmol) 4- amino -4'- ethyl diphenylamines, 2.22 grams of (16.1mmol) potassium carbonate and 100mL toluene, rapidly Stirring, after 90 DEG C of reaction 3h, is down to room temperature, and 10.11 grams of (316mmol) sulphur and 0.04 gram are added in toluene layer (0.35mmol) iodine is warming up to 150 DEG C of reaction 8h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, and Final shielding phenol product is obtained by column chromatography for separation.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.00 (3H), 1.23 (3H), 1.36 (18H), 1.87 (2H), 2.06 (1H), 2.65 (2H), 2.82 (2H), 3.29 (2H), 4.25 (1H), 5.32 (1H), 5.70 (1H), 6.72 (1H), 6.98-7.08 (4H), 7.17 (2H), 7.49 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 15.60,20.3,29.0,29.6,34.6,44.2,113.7,116.1, 118.9,126.2,127.9,129.7,136.6,141.2,146.1,153.4；

C₃₃H₄₄N₂OS₂Calculated value C 72.22, H 8.08, N 5.10, O 2.92, S 11.68；Measured value: C 72.29, H 8.14, N 5.08, O 2.86, S 11.57.

Embodiment 13

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 10.95 grams of (46mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 8.42 grams (48mmol) 1,1,1- trichloromethyl ethane, 18.95 grams of (103mmol) 4-aminodiphenylamines, 0.71 gram of (5.12mmol) potassium carbonate and 150mL benzene stir rapidly, 85 DEG C reaction 1h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains title by column chromatography for separation The shielding phenol product of shown structure.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.01 (3H), 1.36 (18H), 2.89 (2H), 3.03 (4H), 4.25 (2H), 5.32 (1H), 69.7-7.26 (20H), 7.55 (2H)；

¹³C NMR (75MHz, CDCl₃): δ 21.4,29.6,34.6,38.0,43.2,54.0,114.3,118.7,119.3, 121.8,126.2,129.5,132.3,136.5,146.1,149.0,153.4；

C₄₃H₅₂N₄OS calculated value C 76.74, H 7.79, N 8.33, O 2.38, S 4.76；Measured value C 76.69, H 7.73, N 8.45, O 2.32, S 4.71.

Embodiment 14

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 17.98 grams of (89mmol) 1,2- dibromopropanes, 6.62 grams (36mmol) 4-aminodiphenylamine, 0.62 gram of (5.12mmol) potassium carbonate and 150mL isopropanol stir rapidly, anti-at 80 DEG C Answer 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained shown in title by column chromatography for separation The shielding phenol product of structure.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (36H), 1.95 (4H), 3.04 (4H), 3.12 (4H), 5.32 (2H), 6.80-7.26 (13H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 28.5,29.6,34.6,48.4,101.3,116.6,117.1,119.3, 121.8,126.2,129.5,136.5,142.8,146.1,149.1,153.4；

C₄₆H₆₄N₂O₂S₂Calculated value C 74.55, H 8.70, N 3.78, O 4.32, S 8.65；Measured value C 74.59, H 8.73, N 3.67, O 4.35, S 8.64.

Embodiment 15

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 7.70 grams of (36mmol) 2- tert-butyl -4,6- dimercapto phenol of addition, 10.40 grams of (92mmol) 1,2- dichloropropanes, 13.06 grams (71mmol) 4-aminodiphenylamine, 0.43 gram of (3.15mmol) potassium carbonate and 150mL toluene stir rapidly, react at 90 DEG C 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains knot 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), 1.88 (4H), 2.85 (4H), 3.17 (4H), 3.55 (2H), 6.97-7.26 (19H), 7.28 (1H), 7.55 (2H), 8.30 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 28.8,29.2,30.0,31.4,34.5,44.8,45.4,113.5,114.3, 118.9,121.8,122.7,125.3,126.2,129.5,132.3,146.4,149.0,154.9；

C₄₀H₄₆N₄OS₂Calculated value C 72.47, H 6.99, N 8.45, O 2.41, S 9.67；Measured value C 72.52, H 7.03, N 8.37, O 2.43, S 9.64.

Embodiment 16

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 18.56 grams of (78mmol) 2- tert-butyl -4- mercapto-phenols of addition, 10.74 grams of (95mmol) 1,2- dichloropropanes, 11.23 grams (32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine, 0.79 gram of (5.71mmol) potassium carbonate and 150mL Toluene stirs rapidly, in 100 DEG C of reaction 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and leads to It crosses column chromatography for separation and obtains the shielding phenol product of structure shown in title.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (36H), 2.02 (4H), 3.03 (4H), 3.50 (4H), 5.32 (2H), 6.80-7.17 (18H), 7.20 (1H), 7.27 (4H)；

¹³C NMR (75MHz, CDCl₃): δ 28.5,29.6,30.1,31.8,34.6,49.9,92.4,114.0,116.6, 117.1,122.0,126.2,129.2,136.5,142.8,148.7,153.4；

C₅₈H₇₃N₃O₂S₂Calculated value C 76.69, H 8.10, N 4.63, O 3.52, S 7.06；Measured value C 76.61, H 8.05, N 4.71, O 3.49, S 7.03.

Embodiment 17

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 47.16 grams of (45mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 6.48 grams of (51mmol) Isosorbide-5-Nitrae-dichloroetane, 13.78 grams of (53mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamines, 0.86 gram of (8.15mmol) sodium carbonate and 150mL benzene, are stirred rapidly It mixes, in 80 DEG C of reaction 2.5h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column chromatography point From obtaining final shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.88,0.98,1.33,1.40,1.59,1.64,1.73,1.82,1.93, 3.25,3.38,3.71,4.86,6.97,7.02,7.19,7.26,7.55；

¹³C NMR (75MHz, CDCl₃): δ 27.1,28.9,30.1,31.6,32.3,34.5,37.9,43.9,57.1, 114.0,117.7,119.4,121.8,129.5,131.6,144.5,146.1,148.7,155.0.

Embodiment 18

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 29.34 grams of (28mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 2.91 grams of (35mmol) formaldehyde, 6.24 grams (24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, 0.34 gram of (3.2mmol) sodium carbonate and 150mL toluene stir rapidly, 90 DEG C reaction 2h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained finally by column chromatography for separation Shielding phenol product.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 0.86,0.98,1.02,1.40,1.60,1.83,2.59,3.25,3.72, 4.86,6.80,6.97,7.02,7.17,7.26,7.55；¹³C NMR (75MHz, CDCl₃): δ 28.2,30.1,32.3,33.1, 34.5,38.1,49.8,59.1,114.3,119.4,121.8,125.2,122.0,127.3,129.5,132.3,143.3, 146.1,151.3.

Comparative example 1

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.22 grams of (87mmol) formaldehyde, 14.37 grams (85mmol) Diphenylamines and 150mL methanol stir rapidly, in 60 DEG C of reaction 2h.To which after reaction, vacuum distillation removes solvent and generation A small amount of water, and final shielding phenol product is obtained by column chromatography for separation.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H), 7.27(4H)；

¹³C NMR (75MHz, CDCl₃): δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2, 136.6,150.0,153.5；

C₂₇H₃₃NOS calculated value C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measured value: C 77.22, H 7.89, N 3.31, O 3.83, S 7.67.

Comparative example 2

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL methanol stir rapidly, in 70 DEG C of reaction 4h.Wait react knot Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain final shielding phenol product 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 value C 81.43, H 9.53, N 5.76, O 3.29；Measured value: C 81.38, H 9.51, N 5.79, O 3.31.

Comparative example 3

Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyi) phenol of addition, 3.07 grams of (37mmol) formaldehyde, 11.71 grams (45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 4h.To after reaction, subtract A small amount of water of solvent and generation is distilled off in pressure, and obtains final shielding phenol product by column chromatography for separation.

Characterization of The Products data are as follows:

¹H NMR (300MHz, CDCl₃): δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32 (1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；

¹³C NMR (75MHz, CDCl₃): δ 28.7,31.1,34.3,35.7,54.1,117.1,119.4,123.3, 124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；

C₃₆H₄₄N₂OS calculated value C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measured value: C 78.27, H 7.96, N 4.98, O 2.92, S 5.83.

Comparative example 4~7

The composition of the comparative example 4~7 of antioxidant is shown in Table 1.

Table 1

The embodiment 19~28 and comparative example 8~14 of methanol-fueled engine lubricating oil

The embodiment 19~28 of methanol-fueled engine lubricating oil and the formula composition of comparative example 8~14 are shown in Table 2,3.It will In table each component be added to scale reconcile container in, 45 DEG C heating stirring 2 hours, respectively prepare obtain 5W-30/SN Rank methanol-fueled engine lubricant oil composite.

Some lube oil additives used in specific are as follows:

Ashless dispersant: disubstituted polyisobutene succinimide (PIB number-average molecular weight 2300), boronation polyisobutene fourth Imidodicarbonic diamide (PIB number-average molecular weight 1000, boron content 0.5%)；

Detersive: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (TBN400) and middle base number sulfurized alkylphenol calcium (TBN150)；

ZDDP: normal-butyl, 2- ethylhexyl zinc dithiophosphate；

Organic-molybdenum: molybdenum dialkyldithiocarbamacompositions, trade names Molyvan822；

Lubricating base oil: II-6 lubricating base oil, polyolefin synthetic oil PAO6.

Calorimetric test (PDSC) evaluation test embodiment 19~28 is scanned using Pressurized Differential and comparative example 8~14 carries out The high-temperature oxidation resistance of oil product is indicated with the oxidation induction period (unit is min) of test specimen.PDSC test temperature be 220 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.Oxidation induction period is longer, shows the high temperature antioxygen of test specimen It is better to change performance.

Oil is carried out using thin layer oxygen uptake oxidation test (TFOUT) evaluation test embodiment 19~28 and comparative example 8~14 The antioxygenic property of product is indicated with the oxidation induction period (unit is min) of test specimen.The temperature of TFOUT test is 160 DEG C, Using IIIE catalyst, oxygen pressure 620kPa.Oxidation induction period is longer, shows that the antioxygenic property of test specimen is better.

Using engine crankcase coking simulation test testing example 19~28 and the detergency of comparative example 8~14 Energy.This method be by 300ml test specimen be added coking plate analog meter, be heated to 150 DEG C, use continuation mode to temperature for 310 DEG C of aluminium sheet spilled oil is weighed the burnt amount generated on aluminium sheet after 6 hours, is indicated with sediment yield (unit is mg), simulation is lived Deposit beyond the Great Wall.Coking amount is higher, and the detergency for representing this test specimen is poorer.

Table 2

Table 3

The high temperature for carrying out oil product to embodiment 19~28 and comparative example 8~14 using high-frequency reciprocating frictional testing machine is wear-resistant Damage test, experimental condition are as follows: load 1000g, frequency 20Hz, temperature is 100 DEG C, test period 60min.Wear scar diameter is got over Small, coefficient of friction is lower, shows that the anti-wear and wear-resistant performance of test specimen is better.

BRT ball rust test is carried out to embodiment 19~28 and comparative example 8~14, in entire bench test in 18 hours In the process, the metal ball continuous contact acidic liquid and air protected by the test specimen measure metal after the end of the test Spherical reflector intensity obtains gray scale test value, for determining corroded area, thus the resistant to rust ability of qualification test sample.Vinegar Acid/hydrobromic acid/hydrochloric acid/deionized water solution injection rate is 0.19 ml/hour, and air draught is 40 ml/mins, oil Temperature is 48 DEG C.Appraisal result is higher, shows that the rustless property of test specimen is better.

PDSC test, TFOUT test, the test of coking simulation test, high-frequency reciprocating friction test and BRT ball rust test The results are shown in Table 4.

Table 4

From table 4, it can be seen that methanol-fueled engine lubricant oil composite of the present invention has excellent high-temperature oxidation resistance Energy, detergent-dispersant performance energy, preferable abrasion-resistance and lower coefficient of friction and excellent anti-corrosion ability.

Claims

1. a kind of methanol-fueled engine lubricant oil composite comprising shielding phenol, ashless dispersant, metal detergent, ZDDP, has Machine molybdenum and major amount of lubricating base oil, the shielding phenol is as shown in logical formula (I):

In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C_1-300Linear or branched alkyl group, general formula (II) group shown in group shown in and logical formula (III), on condition that at least one group R is group shown in logical formula (II)； Each group R' is same or different to each other, and is each independently selected from hydrogen and C_1-20Linear or branched alkyl group,

In aforementioned each logical formula (II), (III) and (IV), group L, which is selected from, is optionally selected from C by one or more_1-20Alkyl and C_3-20Directly The m+1 valence C that chain or the substituent group of branched heteroalkyl groups replace_2-20Linear or branched alkyl group and optionally by one or more be selected from C_1-20 Alkyl and C_3-20The m+1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces_3-20Linear chain or branched chain miscellaneous alkyl；Group L' is groupWherein group R " is selected from hydrogen, C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl；Each group A it is mutually the same or Difference is each independently selected from Wherein, each group R is same or different to each other, and is each independently selected from hydrogen, C_1-300Directly Group shown in group shown in chain or branched alkyl, logical formula (II) and logical formula (III)；Each group R' is same or different to each other, It is each independently selected from hydrogen and C_1-20Linear or branched alkyl group；A two group R and group-S- occupy surplus on phenyl ring respectively Excess-three position, on condition that at least one group A isM is 1 to 4 integer；Each group R₂It is same or different to each other, is each independently selected from hydrogen, C_1-20Linear or branched alkyl group, logical formula (IV) Shown in group shown in group and logical formula (V)；Each group R_bIt is same or different to each other, is each independently selected from hydrogen and C_1-20Directly Chain or branched alkyl；Each group R_cIt is same or different to each other, is each independently selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20 Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z is 0 to 3 integer；The integer that n is 1 to 8；The integer that n' is 0 to 7, On condition that n'+n≤8；Each group R_dIt is same or different to each other, is each independently selected from group shown in hydrogen and logical formula (V)；Each ring GroupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus, wherein two adjacent cyclic groupsPhenthazine ring is optionally formed with the N atom for bridging the two rings by additional S atom each other, and/or, Two adjacent cyclic groupsOptionally pass through additional group each otherWith bridge the two rings N atom and form 9,10- acridan ring, wherein group R " be selected from hydrogen, C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl,

In logical formula (V), each group A is same or different to each other, and is each independently selected fromWherein each group R It is same or different to each other, is each independently selected from hydrogen, C_1-300Group and general formula shown in linear or branched alkyl group, logical formula (II) (III) group shown in；Each group R' is same or different to each other, and is each independently selected from hydrogen and C_1-20Linear or branched alkyl group； A two group R and group-S- occupy three positions of the residue on phenyl ring respectively；Group L, group R₂, group R_b, group R_c、 Group R_d, cyclic groupAnd y, n, z and m be respectively provided with meaning identical in logical formula (II),

Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure CH₂The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group that obtains, wherein R' be H or C_1-4Linear or branched alkyl group, the shielding phenolic compounds at least one group R in its entire molecular structure_dIt is hydrogen.

2. methanol-fueled engine lubricant oil composite described in accordance with the claim 1, which is characterized in that each group R is respectively only On the spot it is selected from hydrogen, C_1-10Linear or branched alkyl group or number-average molecular weight Mn for 300-3000 polyolefin-based, logical formula (II) institute Group shown in the group shown and logical formula (III)；Each group R' is each independently selected from hydrogen and C_1-4Linear or branched alkyl group；

Group R " is selected from hydrogen, C_1-20Linear or branched alkyl group and C_3-20Linear chain or branched chain miscellaneous alkyl；Each group R₂It selects each independently From hydrogen, C_1-10Group shown in linear or branched alkyl group and logical formula (IV)；Each group R_bIt is each independently selected from hydrogen and C_1-10Straight chain Or branched alkyl；Each group R_cIt is each independently selected from hydrogen, C_1-10Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygen Base；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0 or 1, on condition that n'+n=1 or n'+n=2；Each group R_dFor hydrogen；Each ring GroupSelected from phenyl ring.

3. methanol-fueled engine lubricant oil composite according to claim 2, which is characterized in that group R " be selected from hydrogen, C_1-10Linear or branched alkyl group and C_3-10Linear chain or branched chain miscellaneous alkyl.

4. methanol-fueled engine lubricant oil composite according to claim 2, which is characterized in that each group R_cIn ring GroupThe contraposition of upper nitrogen-atoms.

5. methanol-fueled engine lubricant oil composite according to claim 2, which is characterized in that each group R is respectively only On the spot it is selected from hydrogen and C_1-300Linear or branched alkyl group.

6. methanol-fueled engine lubricant oil composite described in accordance with the claim 1, the shielding phenolic compounds is selected from following Particular compound or its arbitrary proportion mixture:

7. a kind of methanol-fueled engine lubricant oil composite comprising shielding phenol, ashless dispersant, metal detergent, ZDDP, has Machine molybdenum and major amount of lubricating base oil, the manufacturing method of the shielding phenolic compounds include closing phenolate shown in logical formula (X) The first step to react in the presence of amine compounds multi-halogenated compounds shown in general formula (A) shown in object and general formula (Y) Suddenly, optionally further include make the reaction product of the first step reacted with vulcanizing agent and/or with aldehyde compound shown in general formula (Z) The additional step of reaction,

In logical formula (X), each group R₀It is same or different to each other, is each independently selected from hydrogen ,-SH and C_1-300Linear chain or branched chain alkane Base, on condition that at least one group R₀It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C_1-20Straight chain Or branched alkyl,

In general formula (Y), group R'₂Selected from hydrogen, C_1-20Linear or branched alkyl group and groupEach group R_b It is same or different to each other, is each independently selected from hydrogen and C_1-20Linear or branched alkyl group；Each group R_cIt is same or different to each other, respectively From independently selected from hydrogen, C_1-20Linear or branched alkyl group and C_1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z be 0 to 3 integer；The integer that n1 is 1 to 8；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and Naphthalene nucleus,

In general formula (A), group R_haloSelected from optionally by one or more selected from C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl The m1 valence C that substituent group replaces_2-20Linear or branched alkyl group and optionally by one or more be selected from C_1-20Alkyl and C_3-20Straight chain or branch The m1 valence C that the substituent group of chain miscellaneous alkyl replaces_3-20Linear chain or branched chain miscellaneous alkyl, group Halo be halogen, m1 be 2 to 5 integer,

In general formula (Z), group R " is selected from hydrogen, C_1-20Alkyl and C_3-20Linear chain or branched chain miscellaneous alkyl,

Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure CH₂The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group that obtains, wherein R' be H or C_1-4Linear or branched alkyl group.

8. methanol-fueled engine lubricant oil composite according to claim 7, which is characterized in that shown in general formula (Z) Aldehyde compound is formaldehyde；The vulcanizing agent is sulphur；

Each group R₀It is each independently selected from hydrogen ,-SH and C_1-10Linear or branched alkyl group or number-average molecular weight Mn are 300-3000 It is polyolefin-based；Each group R' is each independently selected from hydrogen and C_1-4Linear or branched alkyl group；

Each group R_bIt is each independently selected from hydrogen and C_1-10Linear or branched alkyl group；Each group R_cIt is each independently selected from hydrogen, C_1-10 Linear or branched alkyl group and C_1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic groupSelected from phenyl ring；Group R " is selected from hydrogen, C_1-20Linear or branched alkyl group and C_3-20Linear chain or branched chain miscellaneous alkyl.

9. methanol-fueled engine lubricant oil composite according to claim 8, which is characterized in that each group R_cIn ring GroupThe contraposition of upper nitrogen-atoms.

10. methanol-fueled engine lubricant oil composite according to claim 8, which is characterized in that group R " be selected from hydrogen, C_1-10Linear or branched alkyl group and C_3-10Linear chain or branched chain miscellaneous alkyl.

11. methanol-fueled engine lubricant oil composite according to claim 7, which is characterized in that wherein described In one step, the molar ratio of phenolic compounds shown in the logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.1- 10, the molar ratio of multi-halogenated compounds shown in phenolic compounds and the general formula (A) shown in the logical formula (X) is 1:0.1- 10, in the additional step, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1-10, institute The molar ratio for stating aldehyde compound shown in amine compounds shown in general formula (Y) and the general formula (Z) is 1:0.1-10.

12. methanol-fueled engine lubricant oil composite according to claim 7, which is characterized in that wherein described In one step, the molar ratio of phenolic compounds shown in the logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.5- 5.0, the molar ratio of multi-halogenated compounds shown in phenolic compounds and the general formula (A) shown in the logical formula (X) is 1:0.2- 5.0, in the additional step, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.2- 6.0, the molar ratio of aldehyde compound shown in amine compounds and the general formula (Z) shown in the general formula (Y) is 1:0.5-5.0.

13. methanol-fueled engine lubricant oil composite according to claim 7, which is characterized in that wherein described In one step, the molar ratio of phenolic compounds shown in the logical formula (X) and amine compounds shown in the general formula (Y) is 1:0.8- 2.0, the molar ratio of multi-halogenated compounds shown in phenolic compounds and the general formula (A) shown in the logical formula (X) is 1:0.3- 3.0, in the additional step, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.5- 3.0, the molar ratio of aldehyde compound shown in amine compounds and the general formula (Z) shown in the general formula (Y) is 1:0.8-2.0.

14. according to methanol-fueled engine lubricant oil composite described in one of claim 1-13, which is characterized in that the nothing Grey dispersing agent is selected from polyisobutene succinimide；The metal detergent is selected from sulfonate and/or alkyl monosulfide phenates；It is described ZDDP is selected from C_2-12Alkyl ZDDP；The organic-molybdenum is selected from molybdenum dialkyl-dithiophosphate, dialkyl dithiophosphoric acid oxygen molybdenum, two Alkyl molybdenum dithiocarbamate, xanthic acid molybdenum, Thioxanthate molybdenum, three core molybdenum sulfide complexs, molybdenum amine complex and molybdates esters One of or it is a variety of；The lube base oil be selected from one of API I, II, III, IV and V class lubricating oil base oil or It is a variety of.

15. methanol-fueled engine lubricant oil composite according to claim 14, which is characterized in that the ashless dispersants Agent is selected from disubstituted polyisobutene succinimide and/or boronation polyisobutene succinimide；The metal detergent is selected from Sulfurized alkylphenol calcium；The ZDDP is selected from C_3-8Alkyl ZDDP；The organic-molybdenum is selected from molybdenum dialkyldithiocarbamacompositions.

16. methanol-fueled engine lubricant oil composite according to claim 14, which is characterized in that the shielding phenolate Close the 0.001%-30% that object accounts for the methanol-fueled engine lubricant oil composite gross mass；The ashless dispersant accounts for described The 0.5%-15% of methanol-fueled engine lubricant oil composite gross mass；The metal detergent accounts for the methanol fuel and starts The 0.2%-20% of machine lubricant oil composite gross mass；The ZDDP accounts for the total matter of methanol-fueled engine lubricant oil composite The 0.1%-10% of amount；The organic-molybdenum accounts for the 0.01%-10% of the methanol-fueled engine lubricant oil composite gross mass.

17. methanol-fueled engine lubricant oil composite according to claim 14, which is characterized in that the shielding phenolate Close the 0.05%-20% that object accounts for the methanol-fueled engine lubricant oil composite gross mass；The ashless dispersant accounts for described The 1%-10% of methanol-fueled engine lubricant oil composite gross mass；The metal detergent accounts for the methanol-fueled engine The 0.8%-15% of lubricant oil composite gross mass；The ZDDP accounts for the methanol-fueled engine lubricant oil composite gross mass 0.2%-8%；The organic-molybdenum accounts for the 0.05%-5% of the methanol-fueled engine lubricant oil composite gross mass.

18. methanol-fueled engine lubricant oil composite according to claim 14, which is characterized in that fired in the methanol Expect that pour-point depressant, viscosity index improver, metal corrosion inhibitor, antirust agent and anti-foaming agent are added in engine oil composition One of or it is a variety of.

19. the manufacturing method of methanol-fueled engine lubricant oil composite described in one of claim 1-13, including make described Shield the step of phenol, ashless dispersant, metal detergent, ZDDP, organic-molybdenum and lubricating base oil mix.