CN106590767B - A kind of biodiesel composition and its manufacturing method - Google Patents

A kind of biodiesel composition and its manufacturing method Download PDF

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CN106590767B
CN106590767B CN201510674635.4A CN201510674635A CN106590767B CN 106590767 B CN106590767 B CN 106590767B CN 201510674635 A CN201510674635 A CN 201510674635A CN 106590767 B CN106590767 B CN 106590767B
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straight
hydrogen
branched alkyl
general formula
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CN106590767A (en
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苏朔
段庆华
张辉
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

The present invention relates to a kind of biodiesel composition, including shielding phenolic compounds and major amount of underlying biological diesel oil；The structure of the shielding phenolic compounds is shown in formula (I)：

Description

A kind of biodiesel composition and its manufacturing method
Technical field
The present invention relates to a kind of biodiesel compositions.Specifically, biological bavin can be significantly improved the present invention relates to a kind of The biodiesel composition of oily oxidation stability.
Background technology
As environmental pollution and exhausted two hang-ups of petroleum resources are increasingly taken seriously, biodiesel is as a kind of typical " green energy resource ", because with renewable, cleaning and safe three advantages, it has also become the hot spot of new energy research and development, in recent years Development is very rapid.
Biodiesel refers to by animal and plant fat (fatty acid triglycercide) and alcohol (methanol or ethyl alcohol) through ester exchange reaction Obtained aliphatic acid monoalkyl ester, most typically fatty acid methyl ester.Biodiesel is mainly with oil plants such as soybean and rapeseed The grease and animal fat of the oil plants water plants such as the oil-yielding shrubs such as crop, oil palm and Chinese pistache fruit, engineering microalgae, useless meal Drink oil etc. makees raw material.
Biodiesel is because containing more unsaturated fatty acid methyl ester, such as methyl oleate, methyl linoleate, leukotrienes first Ester etc., compared with petrifaction diesel, oxidation stability is very poor, is very easy to oxidation deterioration, this using and storing to biodiesel It deposits and all causes very big difficulty.Degree of unsaturation is bigger, and oxidation stability is poorer.In physical holding of the stock, by air, illumination and metal The effect of the conditions such as ionic impurity, unsaturated fat methyl esters aoxidizes in biodiesel, generation peroxide, fatty alcohol, aldehyde, The products such as ketone, organic acid and water further generate oligomer, form colloid, greasy filth etc..The high activity peroxide of generation Becoming fragile it will cause rubber components aging and fuel is caused to leak, the organic acid of generation easily causes engine metal component corrosion, The colloid and greasy filth of formation can cause filter net jam and jet pump coking in engine, and cause smoke evacuation increase, difficulty in starting.Cause This, oxidation stability is one of important quality index of biodiesel.
European Biodiesel Standards EN14214：2003rd, Australian Biodiesel Standards (Draft2003), New Zealand's life Object diesel oil standard NZS7500：2005th, Brazil Biodiesel Standards ANP255 (2003), India Biodiesel Standards IS15607： 2005th, South Africa Biodiesel Standards SANS1935：2004 and China's diesel fuel blending with biodiesel (BD100) country Standard GB/T 20828-2007 all provide the oxidation stability of biodiesel for the induction period at 110 DEG C it is small not less than 6 when, survey Method is determined for EN14112：2003.
Seek more efficiently antioxidant additive and research and development application in biodiesel, be always those skilled in the art's effort Target.
United States Patent (USP) US 5304314 discloses a kind of phenolic compounds for being suitable as sulfur-bearing that antioxidant uses and arylamine. United States Patent (USP) US 2006/0189824A1 disclose a kind of conjunction of the shielding phenolate containing secondary aromatic amine for being suitable as antioxidant and using Object.
But the compound of these prior arts in biodiesel in use, the antioxygenic property and detergency of oil product Room for improvement can be still remained.
Therefore, the prior art is still required for a kind of biodiesel composition, not only has excellent oxidation stability, And also show excellent cleansing performance.
The content of the invention
The present invention relates to the contents of following aspect.
1. a kind of biodiesel composition, including shielding phenolic compounds and major amount of underlying biological diesel oil；
It is described shielding phenolic compounds structure be：
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), the base shown in logical formula (II) Group shown in group and logical formula (III), on condition that at least one group R is the group shown in logical formula (II)；Each group R' is each other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight chain Or branched alkyl),
In foregoing each logical formula (II), (III) and (IV), each group L is same or different to each other, and is group independentlyWherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20Linear chain or branch chain is miscellaneous Alkyl is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain miscellaneous alkyl；Each group R2It is mutually the same or not Together, hydrogen, C are each independently selected from1-20Group shown in straight or branched alkyl, logical formula (IV) and the group shown in logical formula (V) (preferably it is each independently selected from hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV))；Each group RbIt is mutually the same Or it is different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight chain or branch Alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain or Branched alkyl oxygroup (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup, It 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)；N is 1 to 8 integer (preferably 1 or 2)；N' is 0 to 7 integer (preferably 0,1 or 2), on condition that n'+n≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same or different to each other, is each independently selected from shown in hydrogen and logical formula (V) Group (preferably hydrogen)；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus (preferably benzene Ring), wherein two adjacent cyclic groupsOptionally pass through the N atoms of the two rings of additional S atom and bridge joint each other And formed phenthazine ring and/or, adjacent two cyclic groupsOptionally pass through additional group each other (wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl, preferably Selected from hydrogen and C1-10Straight or branched alkyl) and bridge the N atoms of the two rings and form 9,10- acridan rings,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), the base shown in logical formula (II) Group shown in group and logical formula (III) (is preferably each independently selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' that This is identical or different, is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Directly Chain or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain Miscellaneous alkyl；A is 0 or 1, an and two group R and group-(S)a- L- occupies three positions of residue on phenyl ring respectively,
Wherein, the linear chain or branch chain miscellaneous alkyl is selected from the one or more inside straight or branched alkyl molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- by selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain Or branched alkyl) one of the substituting group group and straight or branched alkyl molecular structure that directly substitute and obtain inside one A or multiple (such as 1 to 3,1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining, The wherein shielding phenolic compounds at least one group R in its entire molecular structuredIt is hydrogen.
2. according to the shielding phenolic compounds described in any preceding aspect, selected from following particular compound or its arbitrary proportion Mixture：
3. a kind of biodiesel composition, including shielding phenolic compounds and major amount of underlying biological diesel oil, the shielding The manufacturing method of phenolic compounds includes making the phenolic compounds shown in logical formula (X) and the amine compounds shown in general formula (Y) at general formula (Z) The first step to react in the presence of shown aldehyde compound (preferably formaldehyde), optionally further including makes the first step Reaction product reacts with vulcanizing agent (preferably sulphur) and/or reacts additional with the aldehyde compound (preferably formaldehyde) shown in general formula (Z) Step,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branch chain Alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), on condition that at least one A group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably It is each independently selected from hydrogen and C1-4Straight or branched alkyl),
In general formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbEach other It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight chain Or branched alkyl)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly Chain or branched alkyl oxygroup (are preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygen Base is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；Z be 0 to 3 it is whole Number (preferably 0 or 1)；N1 is 1 to 8 integer (preferably 1 or 2)；Each cyclic groupIt is same or different to each other, it is each independent Ground is selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20Straight chain or branch Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain miscellaneous alkyl,
Wherein, the linear chain or branch chain miscellaneous alkyl is selected from the one or more inside straight or branched alkyl molecular structure (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2- by selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain Or branched alkyl) one of the substituting group group and straight or branched alkyl molecular structure that directly substitute and obtain inside one A or multiple (such as 1 to 3,1 to 2 or 1) group-CH<By substituting group-N<The group for directly substituting and obtaining.
4. according to the 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 the molar ratios of amine compounds be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:The molar ratio of 0.8-2.0, the phenolic compounds shown in the logical formula (X) and the aldehyde compound shown in the general formula (Z) is 1: 0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8-2.0, in the additional step, the amine compounds shown in the general formula (Y) The molar ratio of object and the vulcanizing agent is 1:1-10, preferably 1:1.2-6.0 more preferable 1:1.5-3.0, shown in the general formula (Y) Amine compounds and the general formula (Z) shown in the molar ratio of aldehyde compound be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0。
5. in the biodiesel composition described in any preceding aspect, the shielding phenolic compounds is in the biodiesel Content is 10~50000mg/kg, preferably 20~10000mg/kg, more preferable 30~5000mg/kg in composition；
The biodiesel refers to grease and low-carbon alcohols (such as C1~C5Fatty alcohol) react and generate through transesterification (alcoholysis) The transesterification product of fatty acid ester of low-carbon alcohol, generally fatty acid methyl ester, i.e. grease and methanol.
The trans-esterification processes can be any known or unknown by grease and the ester exchange reaction of low-carbon alcohols Obtain the process of biodiesel, such as acid catalyzed process, base catalysis method, enzyme catalysis method, supercritical methanol technology, etc..Can specifically it join Examine the documents such as CN1473907, DE3444893, CN1472280, CN1142993, CN1111591, CN1594504.
The grease has general sense well known in the art, is the general name of oil and fat, main component is fatty acid glycerine Three esters.General room temperature is the oil that is known as of liquid, and room temperature is being known as fatty (abbreviation fat) for solid or semisolid.The grease includes Vegetable oil and animal oil, in addition, further include the oil plant in the substances such as microorganism, algae or even can also be waste oil, Such as waste cooking oil, gutter oil, swill oil, used grease or the rotten grease such as acidification oil of grease factory.The plant Oil can be that herbaceous plant oil can also be xylophyta oil, such as peanut oil, corn oil, cottonseed oil, rape seed oil, soybean oil, palm fibre Palmitic acid oil, safflower oil, linseed oil, coconut oil, Oak Tree oil, apricot kernel oil, walnut oil, castor oil, sesame oil, olive oil, tall oil (Tall Oil), sunflower oil, curcas oil, tung oil, shinyleaf yellowhorn oil, coptis wood oil, halophytes such as kostelezkya virginica, cyperue esculentus Wait the oil of plants.The animal oil can be lard, chicken fat, duck oil, goose oil, sheep oil, house oil, butter, haco oil, shark oil Deng.
In the biodiesel can also contain selected from petroleum diesel, Fiscber-Tropscb synthesis diesel oil, be hydrocracked biodiesel with And the one or more in oxygen-containing diesel oil blending component.Wherein, the petroleum diesel refers to crude oil (oil) through each of oil plant Kind of refining process such as Atmospheric vacuum, catalytic cracking, coking, hydrofinishing, the devices such as are hydrocracked treated boiling range at catalytic reforming Fraction between 160~380 DEG C, and meet light diesel fuel standard GB/T 252-2000 or derv fuel by what allotment formed The compression ignition engine fuel of standard GB/T/T 19147-2003.The Fiscber-Tropscb synthesis diesel oil refer mainly to natural gas or The GTL diesel oil (Gas To Liquid) or CTL diesel oil (Coal To that coal produces for raw material through Fischer-Tropsch (F-T) synthetic method Liquid), it can also be the BTL diesel oil (Biomass To Liquid) that plant fiber is produced through Fischer-Tropsch synthetic method.Institute Fiscber-Tropscb synthesis diesel oil is stated substantially free of sulphur and aromatic hydrocarbons, is very clean fuel, but its lubricity is very poor, with biological bavin Lubricity substantially improves after oil blending, but the oxidation stability of blending fuel is it is possible that be deteriorated, therefore the blending containing biodiesel Fuel is also required to add in antioxidant.The biodiesel that is hydrocracked is also referred to as second generation biodiesel, refers to by vegetable and animals oils Fat is by being hydrogenated with and being generated after cracking reaction with C8~C24Based on alkane, especially with C12~C20N-alkane for mainly into The reaction product divided, this to be hydrocracked biodiesel Cetane number height, sulphur and arene content are extremely low, are fired as diesel engine Material or blending component can substantially reduce the discharge of diesel oil organic pollutants.Oxygen-containing diesel oil blending component refers to fire with various diesel engines Material is deployed into the mixture of the oxygenatedchemicals or oxygenatedchemicals that meet certain code requirement, be typically alcohols and ethers or its Mixture, alcohols such as C1~C18Fatty alcohol, preferably C1~C12Unitary fatty alcohol, as methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, Hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecylenic alcohol, laruyl alcohol and its various isomers, ethers can be dimethyl ether, methyl Tertbutyl ether, ethyl tert-butyl ether (ETBE), C6~C14Aliphatic alcohol polyethenoxy (propylene) ether, C6~C14Alkylphenol-polyethenoxy (propylene) Ether, polyoxymethylene dimethyl ether (Polyoxymethylene Dimethyl Ethers, CH3O(CH2O)xCH3, x=1~8) Deng and its mixture.
Antioxidant, cetane improver, detersive, scattered can also be added in the biodiesel composition of the present invention One or more additives in agent, pour-point depressant, viscosity index improver, metal deactivator, antirust agent and anti-foaming agent.These add Agent is added to can be used alone, can also combination of two or more use, and its dosage is from the conventional amount used of this field, not It is special to limit.
6. the manufacturing method of the biodiesel composition of any preceding aspect, including making the shielding phenol and the basis raw The step of object diesel oil mixes.
Technique effect
Shielding phenolic compounds according to the present invention compared with the compound of the prior art, shows the antioxygen significantly improved Change performance (thermal stability), the oxidation stability of such as diesel oil can be effectively improved.
Shielding phenolic compounds according to the present invention in a preferred embodiment, is showing excellent antioxygenic property While, also exhibit further excellent cleansing performance (i.e. deposit generation rejection).This is prior art compound Not available.
The biodiesel composition of the present invention shows excellent antioxygenic property and cleansing performance.
Specific embodiment
The specific embodiment of the present invention is described in detail below, it should be noted however that the protection of the present invention Scope is not limited to these specific embodiments, 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 contains with what those skilled in the art routinely understood 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, but also include also being of little use at present, will but become art-recognized is suitable for those similar to purpose.
In the context of the present specification, in addition to the content clearly stated, any matters or item do not mentioned are equal Directly be applicable in it is known in the art those 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 technological thought formed therefrom regards For the original disclosure of the present invention or a part for 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 apparent 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 branch chain Alkyl, linear chain or branch chain alkenyl, linear chain or branch chain alkynyl, cycloalkyl, cycloalkenyl group, cycloalkynyl radical, aryl or its combination group, wherein It is preferred that straight or branched alkyl, linear chain or branch chain alkenyl, aryl or its combination group.It, specifically such as can be with as the alkyl Enumerate C1-20Alkyl, including C1-20Straight or branched alkyl, C2-20Linear chain or branch chain alkenyl, C2-20Linear chain or branch chain alkynyl, C3-20 Cycloalkyl, C3-20Cycloalkenyl group, C3-20Cycloalkynyl radical, C6-20Aryl or its combination group, wherein it is preferred that C1-20Straight or branched alkyl, C6-20Aryl or its combination group.As the combination group, for example one or more C can be enumerated1-20Straight or branched alkyl (preferably one or more C1-10Straight or branched alkyl) and one or more C6-20Aryl (preferably one or more phenyl or naphthalene Base) group that is obtained by Direct Bonding.As the combination group, for example it can further enumerate one or more C1-10Straight chain Or branched alkyl phenyl, phenyl C1-10Straight or branched alkyl or one or more C1-10Straight or branched alkyl phenyl C1-10Straight chain Or branched alkyl etc., wherein more preferable C1-10Straight or branched alkyl phenyl (such as tert-butyl-phenyl), phenyl C1-10Straight chain or branch Alkyl group (such as benzyl) or C1-10Straight or branched alkyl phenyl C1-10Straight or branched alkyl (such as t-butylbenzyl).
In the context of the present invention, so-called " linear chain or branch chain miscellaneous alkyl ", refers to straight or branched alkyl 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-CH2- by selected from-O- ,-S- and-NR'-, (R' is H or C1-4One of straight or branched alkyl) The substituting group group or straight or branched alkyl molecular structure that directly substitute and obtain inside (not including the alkyl point 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<The group for directly substituting and obtaining.As the substituting group, preferably-O- or-S-, more preferable-S-.Obviously , for the angle of structural stability, there are it is multiple when, not Direct Bonding between these substituting groups.Though in addition, The carbon number of the right straight or branched alkyl is because group-CH2- or group-CH<It is accordingly reduced by replacement, but for table Simplicity is stated, still refers to the linear chain or branch chain miscellaneous alkyl with the carbon number of the replacement foregoing description straight or branched alkyl Carbon number.As the linear chain or branch chain miscellaneous alkyl, for concrete example, C4Straight chained alkyl is such as(group in formula indicated by arrow is not in inside molecular structure, but is located In the end of main chain) it is directly substituted acquisition-CH by a substituting group-O-2-O-CH2-CH3Or-CH2-CH2-O-CH3, it is referred to as For C4Linear heteroalkyl group.Alternatively, C4Branched alkyl is such as(the base in formula indicated by arrow Group is not in inside molecular structure, but the end in main chain and side chain) by a substituting group-N<Directly substituting will obtainReferred to as C4Branched heteroalkyl groups.According to the present invention, as the miscellaneous alkane of the linear chain or branch chain Base, for example C can be enumerated3-20Linear chain or branch chain miscellaneous alkyl, wherein it is preferred that C3-10Linear chain or branch chain miscellaneous alkyl or C3-6Straight chain or Branched heteroalkyl groups.
In the context of the present specification, expression way " number+valency+group " or its referred to similar to term from the group Remove what is obtained after the hydrogen atom of the quantity representated by the number in corresponding foundation structure (such as chain, ring or its combination etc.) Group preferably refers to remove from the carbon atom (preferably saturated carbon atom and/or non-same carbon atom) contained by the structure The group obtained after the hydrogen atom of quantity representated by the number.For example, " trivalent straight or branched alkyl " is referred to from straight The group for removing 3 hydrogen atoms on chain or branched paraffin (the basic chain i.e. corresponding to the straight or branched alkyl) and obtaining, and " divalent linear chain or branch chain miscellaneous alkyl " then refer to from the miscellaneous alkane of linear chain or branch chain (preferably from the carbon atom contained by the miscellaneous alkane or Person is further, from non-same carbon atom) on remove 2 hydrogen atoms and the group that obtains.
In the case where not clearly indicating, all percentages for being previously mentioned in this specification, number, ratio etc. be all with On the basis of weight, unless on the basis of weight when, does not meet the conventional understanding of those skilled in the art.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration What chromatography (GPC) measured.
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 spectrograms is：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 the shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), there are it is multiple when, each group R is same or different to each other, independently Selected from hydrogen, C1-300Group shown in straight or branched alkyl, logical formula (II) and the group shown in logical formula (III), on condition that at least One group R is the group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Straight or branched alkyl, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Straight or branched alkyl, more preferable C1-4Straight or branched alkyl) or it is polyolefin-based.As Described polyolefin-based, it is the polyolefin-based of 300-3000 that specifically can such as enumerate number-average molecular weight Mn.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, it is described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depending on the species or the polyolefin of the polyolefin as starting material The difference of manufacturing method may also contain a small amount of olefinic double bond in the polyolefin-based strand and (for example be manufactured in polyolefin 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 this " alkyl ".
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 is described polyolefin-based, the other is hydrogen, C1-20Straight chain or branch Alkyl group (preferably C1-10Straight or branched alkyl) 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), there are it is multiple when, each group R' is same or different to each other, independently Selected from hydrogen and C1-20Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (I), there are it is multiple when, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Straight or branched alkyl.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20 Straight or branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (II), in the definition of group L, group R " be selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain miscellaneous alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Shown in straight or branched alkyl, logical formula (IV) Group shown in group and logical formula (V).
According to embodiment of the present invention, in logical formula (II), group R2Selected from hydrogen, C1-10Straight or branched alkyl With the group shown in logical formula (IV).
According to the present invention, in logical formula (II), there are it is multiple when, each group RbIt is same or different to each other, it is each independent Ground is selected from hydrogen and C1-20Straight or branched alkyl is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (II), there are it is multiple when, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably hydrogen.
According to the present invention, in logical formula (II), there are it is multiple when, each group RcIt is same or different to each other, it is each independent Ground is selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (II), there are it is multiple when, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (II), a preferably group RcIn cyclic group Upper N atoms (that is, with group RdThe N atoms of bonding) contraposition.
According to the present invention, in logical formula (II), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), n is 1 to 8 integer, preferably 1 or 2.
According to the present invention, in logical formula (II), there are it is multiple when, each group RdIt is same or different to each other, it is each independent Ground is selected from the group shown in hydrogen and logical formula (V), preferably hydrogen.
According to the present invention, in logical formula (II), there are it is multiple when, each cyclic group(in the knot of logical formula (II) 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 logical formula (II) 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 logical formula (II)), In preferred phenyl ring.
According to embodiment of the present invention, in logical formula (II), adjacent two cyclic groupsEach other may be used With by additional S atom (not shown in structural formula) and bridge the two rings N atoms (that is, with group RdThe N of bonding is former Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsIn each with another adjacent cyclic groupForm the phenthazine ring.
According to embodiment of the present invention, in logical formula (II), adjacent two cyclic groupsEach other may be used To pass through additional group(not shown in structural formula) and bridge the two rings N atoms (that is, with group RdThe N atoms of bonding) and form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain or Branched alkyl.
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridans ring is formed, must not It is required that these cyclic groupsIn each with another adjacent cyclic groupForm the 9,10- Acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl is (preferably C1-20Straight or branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (III), in the definition of group L, group R " be selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain miscellaneous alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Shown in straight or branched alkyl, logical formula (IV) Group and logical formula (V) shown in group.
According to embodiment of the present invention, in logical formula (III), group R2Selected from hydrogen, C1-10Straight or branched alkyl With the group shown in logical formula (IV).
According to the present invention, in logical formula (III), there are it is multiple when, each group RbIt is same or different to each other, it is each independent Ground is selected from hydrogen and C1-20Straight or branched alkyl is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (III), there are it is multiple when, each group RbIt is mutually the same Or it is different, it is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably hydrogen.
According to the present invention, in logical formula (III), there are it is multiple when, each group RcIt is same or different to each other, it is each independent Ground is selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (III), there are it is multiple when, each group RcIt is mutually the same Or it is different, it is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (III), a preferably group RcIn cyclic groupUpper N atoms (that is, with group RdThe N atoms of bonding) contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), n is 1 to 8 integer, preferably 1 or 2.
According to the present invention, in logical formula (III), there are it is multiple when, each group RdIt is same or different to each other, it is each independent Ground is selected from the group shown in hydrogen and logical formula (V), preferably hydrogen.
According to the present invention, in logical formula (III), there are it is multiple when, each cyclic group(in logical formula (III) 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 knot of logical formula (III) 1,4- phenylenes are rendered as inside structure) and naphthalene nucleus (be preferably rendered as 1,4- or 2,6- Asias 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), adjacent two cyclic groupsEach other may be used With by additional S atom (not shown in structural formula) and bridge the two rings N atoms (that is, with group RdThe N of bonding is former Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsIn each with another adjacent cyclic groupForm the phenthazine Ring.
According to embodiment of the present invention, in logical formula (III), adjacent two cyclic groupsEach other Additional group can be passed through(not shown in structural formula) and bridge the two rings N atoms (that is, with base Group RdThe N atoms of bonding) and form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain Or branched alkyl.
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridans ring is formed, must not It is required that these cyclic groupsIn each with another adjacent cyclic groupFormed this 9, 10- acridan rings.
According to the present invention, in logical formula (IV), there are it is multiple when, each group RbIt is same or different to each other, it is each independent Ground is selected from hydrogen and C1-20Straight or branched alkyl is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (IV), there are it is multiple when, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably hydrogen.
According to the present invention, in logical formula (IV), there are it is multiple when, each group RcIt is same or different to each other, it is each independent Ground is selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (IV), there are it is multiple when, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in logical formula (IV), a preferably group RcIn cyclic groupUpper N atoms (that is, with group RdThe N atoms of bonding) contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), n' is 0 to 7 integer, preferably 0,1 or 2, on condition that n'+n≤8.According to An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical with the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), there are it is multiple when, each group RdIt is same or different to each other, it is each independent Ground is selected from the group shown in hydrogen and logical formula (V), preferably hydrogen.
According to the present invention, in logical formula (IV), there are it is multiple when, each cyclic group(in logical formula (IV) Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV) Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)), Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (IV), adjacent two cyclic groupsEach other Can by additional S atom (not shown in structural formula) and bridge the two rings N atoms (that is, with group RdThe N of bonding is former Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that These cyclic groupsIn each with another adjacent cyclic groupForm the phenthazine Ring.
According to embodiment of the present invention, in logical formula (IV), adjacent two cyclic groupsEach other Additional group can be passed through(not shown in structural formula) and bridge the two rings N atoms (that is, with base Group RdThe N atoms of bonding) and form 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or Branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain Or branched alkyl.
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridans ring is formed, is not had These cyclic groups of exclusive requirementIn each with another adjacent cyclic groupIt is formed The acridan ring.
According to the present invention, in logical formula (V), there are it is multiple when, each group R is same or different to each other, independently Selected from hydrogen, C1-300Group shown in straight or branched alkyl, logical formula (II) and the group shown in logical formula (III).
According to embodiment of the present invention, in logical formula (V), there are it is multiple when, each group R is mutually the same or not Together, hydrogen and C are each independently selected from1-300Straight or branched alkyl.
According to the present invention, in logical formula (V), as the C1-300Straight or branched alkyl, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Straight or branched alkyl, more preferable C1-4Straight or branched alkyl) or it is polyolefin-based.As Described polyolefin-based, it is the polyolefin-based of 300-3000 that specifically can such as enumerate number-average molecular weight Mn.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, it is described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depending on the species or the polyolefin of the polyolefin as starting material The difference of manufacturing method may also contain a small amount of olefinic double bond in the polyolefin-based strand and (for example be manufactured in polyolefin 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 this " alkyl ".
According to embodiment of the present invention, in logical formula (V), there are multiple group R, one of group R is institute State it is polyolefin-based, the other is hydrogen or C1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl, more preferable C1-4Directly Chain or branched alkyl).
According to embodiment of the present invention, in logical formula (V), when group R is described polyolefin-based, the polyolefin Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), there are it is multiple when, each group R' is same or different to each other, independently Selected from hydrogen and C1-20Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (V), there are it is multiple when, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Straight or branched alkyl.
According to the present invention, in logical formula (V), group L is group
According to the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20 Straight or branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (V), in the definition of group L, group R " be selected from hydrogen, C1-10Straight or branched alkyl and C3-10Linear chain or branch chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen And C1-10Straight or branched alkyl.
According to the present invention, in logical formula (V), two group R and a group-(S)a- L- occupies benzene in logical formula (V) respectively Three positions of residue on ring.
According to the present invention, in logical formula (V), a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula (V) shown in), it is necessary to include structureAs phenol unit.According to a preferred embodiment of the present invention, the screen It covers phenolic compounds and at most 5, at most 3, at most 2 or at most 1 phenol units is included in its entire molecular structure.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (II) or further as logical Formula (III) or (IV) are shown), it is necessary to include structureAs amine unit.One according to the present invention Preferred embodiment, it is described shielding phenolic compounds in its entire molecular structure comprising at most 15, at most 10, at most 8 A, at most 6, at most 4, at most 3 or at most 2 amine units.
According to the present invention, it is described shielding phenolic compounds in its entire molecular structure preferably at least there are one (preferably 2,3 It is a or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure Have at least one in following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units, Cyclic groupIt is identical with the definition in logical formula (II) with group R ".
A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely A few hydrogen amine unit (1).
Specifically, to shield phenolic compoundsExemplified by, the compound is in its entire molecule knot Comprising 2 phenol units and 2 amine units in structure, and include 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, the 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 exist in the form of the mixture (in any proportion) of wherein two or more, manufacture or It uses, this has no effect on the realization of effect of the present invention.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can pass through following manufacturing method system It makes, but is not limited thereto.
Manufacturing method according to the present invention, including making the phenolic compounds shown in logical formula (X) and the amination shown in general formula (Y) Close the first step that object reacts in the presence of the aldehyde compound shown in general formula (Z).
According to the present invention, lead to formula (X) in, there are it is multiple when, each group R0It is same or different to each other, selects independently From hydrogen ,-SH and C1-300Straight or branched alkyl, on condition that at least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Straight or branched alkyl, for example C can be enumerated1-20Directly Chain or branched alkyl (preferably C1-10Straight or branched alkyl, more preferable C1-4Straight or branched alkyl) or it is polyolefin-based.As Described polyolefin-based, it is the polyolefin-based of 300-3000 that specifically can such as enumerate number-average molecular weight Mn.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, it is described polyolefin-based (basic On) it is saturation (being rendered as chain alkyl structure), but depending on the species or the polyolefin of the polyolefin as starting material The difference of manufacturing method may also contain a small amount of olefinic double bond in the polyolefin-based strand and (for example be manufactured in polyolefin 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 this " alkyl ".
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 described polyolefin-based, the other is hydrogen or C1-20Straight or branched alkyl is (preferably C1-10Straight or branched alkyl).
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), there are it is multiple when, each group R' is same or different to each other, independently Selected from hydrogen and C1-20Straight or branched alkyl.
According to embodiment of the present invention, in logical formula (X), there are it is multiple when, each group R' it is mutually the same or Difference is each independently selected from hydrogen and C1-4Straight or branched alkyl.
According to the present invention, as the logical formula (X) shown in phenolic compounds, can directly use commercially available product, also may be used 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 combination of two or more use.
According to the present invention, the manufacturing method as the phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl In the presence of changing catalysts, making the phenolic compounds shown in general formula (X') and polyolefin, (number-average molecular weight Mn is 300-3000, excellent Select 500-2000, more preferable 500-1500) occur alkylated reaction method.
According to the present invention, in general formula (X'), group R' has the meaning identical with 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, the 3rd group R'0It is hydrogen ,-SH or C1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl).
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 in 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 as obtained from 1- butylene or isobutylene homopolymerisation polymer and by 1- butylene, 2- butylene and different Prepared by passing through copolymerization two or three in butylene polymer.The commercial product of such polymer may also be contained negligible Other olefinic components of amount, but this has no effect on the implementation of the present invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB) is also referred to as high reaction activity and gathers Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) Belong to double bond to be provided by methyl ethenylidene.
As the catalyst for alkylation reaction, for example Lewis acid catalysts can be enumerated, for example, selected from alchlor, Boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network The one or more in object are 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, most preferably preferably 1h-8h, 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 carry out in the presence of the solvent.As the solvent, such as can be with Enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably Use hexane.
According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute The phenolic compounds shown.
According to the present invention, in general formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and group
According to the present invention, in general formula (Y), there are it is multiple when, each group RbIt is same or different to each other, independently Selected from hydrogen and C1-20Straight or branched alkyl is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl.
According to embodiment of the present invention, in general formula (Y), there are it is multiple when, each group RbIt is mutually the same or Difference is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably hydrogen.
According to the present invention, in general formula (Y), there are it is multiple when, each group RcIt is same or different to each other, independently Selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in general formula (Y), there are it is multiple when, each group RcIt is mutually the same or Difference is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup.
According to embodiment of the present invention, in general formula (Y), a preferably group RcIn cyclic groupUpper N atoms (that is, with group RdThe N atoms 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), n1 be 1 to 8 integer, preferably 1 or 2.
According to the present invention, in general formula (Y), there are it is multiple when, 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 the general formula (Y) shown in amine compounds, can directly use commercially available product, not There is special limitation.In addition, the amine compounds shown in as the general formula (Y), can be used only one kind, it can also be two kinds or more Kind is applied in combination.
According to the present invention, in general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20Linear chain or branch chain miscellaneous alkyl.
According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C1-10Straight or branched alkyl And C3-10Linear chain or branch chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C1-10Linear chain or branch chain Alkyl.
According to the present invention, as the general formula (Z) shown in aldehyde compound, for example C can be enumerated1-6Aliphatic aldehyde and benzene Formaldehyde.
According to embodiment of the present invention, as the C1-6Aliphatic aldehyde, for example C can be enumerated1-6Straight chain or branch Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can use its aqueous solution, Paraformaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, as the general formula (Z) shown in aldehyde compound, can be used only one kind, can also two kinds or Multiple combinations use.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula (X) molar ratio of phenolic compounds and the amine compounds shown in the general formula (Y) shown in 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 and the aldehyde compound shown in the general formula (Z) shown in is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the first step can depositing in solvent In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..These solvents can be used only one kind, can also combination of two or more make With.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, can be added without Catalyst can also add in catalyst.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid etc. can be enumerated.As the organic acid catalyst, than Pyrovinic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.
As the dosage of the catalyst, can be not particularly limited directly with reference to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the first step There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the first step There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the first step terminates, pass through Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step Reaction mixture) in remove the volatile materials such as solvent that may be present after, you can obtain the reaction product of first step.
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds, which optionally further includes, makes described the The reaction product of one step and the additional step (hereinafter referred to as additional step A) of vulcanizing agent reaction (forming phenthazine ring).
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds, which optionally further includes, makes described the The reaction product of one step and the extra step of the aldehyde compound reaction (forming acridan ring) shown in aforementioned formula (Z) Suddenly (hereinafter referred to as additional step B).
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can be only carried out, The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both 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, the additional step is carried out again after additional step A terminates B first carries out the additional step B, and the additional step A is carried out again after additional step B terminates.It is in addition, each attached Product (that is, the 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 not also pass through the separation, and it is straight It connects and is used to carry out the additional step A in the form of the reaction mixture of the first step.Alternatively, the additional step A It can be carried out after the additional step B terminates.When the additional step A the additional step B terminate after carry out when, The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.Or Person, the reaction product of the additional step B can not also pass through the separation, and directly be mixed with the reaction of the additional step B The form of object is used to carry 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 etc. can be enumerated, 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 and the vulcanizing agent shown in is generally 1:1-10, preferably 1:1.2-6.0 more preferable 1:1.5- 3.0。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can depositing in solvent In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene, Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide, Dimethyl acetamide and N-Methyl pyrrolidone) etc..These solvents can be used only one kind, can also combination of two or more make 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 with reference 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, you can obtain the reaction product of additional step A or the separation can not also be passed through, 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 can carry out (as independent step), can also be carried out at the same time with the first step after the first step terminates, It is not particularly limited.When the additional step B the first step terminate after carry out when, the first step it is anti- Product is answered to be separated as previously described from the reaction mixture of the first step.Alternatively, the first step is anti- Answer product that can not also pass through the separation, and it is described attached for carrying out directly in the form of the reaction mixture of the first step Add step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When the additional step B exists When the additional step A is carried out after terminating, the reaction product of the additional step A is as described herein from the extra step It is separated in the reaction mixture of rapid A.Alternatively, the reaction product of the additional step A can not also pass through the separation, and it is straight It connects and is used to carry out the additional step B in the form of the reaction mixture of the additional step A.In addition, as the additional step B When being carried out at the same time with the first step, directly into the reaction system of the first step (such as in the first step Start or during first step progress) add the hydroformylation shown in the general formula (Z) according to hereinafter provided dosage Close object.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, as described Aldehyde compound shown in general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, than C can such as be enumerated1-6Linear chain or branch chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, For example its aqueous solution, paraformaldehyde or paraformaldehyde form can be used, it is not particularly limited.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, the general formula (Y) molar ratio of amine compounds and the aldehyde compound shown in the general formula (Z) shown in is generally 1:0.1-10, preferably 1:0.5- 5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B is (as individual step During rapid progress) it can carry out in the presence of the solvent.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as second Nitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and oil Ether), C1-6Aliphatic alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as two Chloromethanes, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10 Amide (such as dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, It can also combination of two or more use.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual When step carries out) in, catalyst can be added without, catalyst can also be added in.As the catalyst, for example nothing can be enumerated Machine acid catalyst and organic acid catalyst.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid etc. can be enumerated. As the organic acid catalyst, for example pyrovinic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid etc. can be enumerated.Make For the dosage of the catalyst, can be not particularly limited directly with reference to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual When step carries out) there is no particular limitation reaction time, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h- 6h。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual When step carries out) reaction temperature there is no particular limitation, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 ℃-120℃。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual When step carries out) terminate after, the reaction that is obtained by conventionally known separation method (such as evaporation etc.) from additional step B After removing the volatile materials such as solvent that may be present in mixture, you can obtain the reaction product of additional step B, Huo Zheye Subsequent reaction step can be directly used in without the separation (than additional step A as the aforementioned).
It is known in the art, foregoing 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, in the manufacturing method of the shielding phenolic compounds, reaction product as the first step, 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 (such as shielding phenolic compounds shown in aforementioned formula (I)) or the mixture for including 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 the shielding phenolic compounds of the present invention without distinction in bright book context.In consideration of it, according to The present invention, and there is no these reaction products are further purified or a certain spy is further separated out 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 through column chromatography method or the reaction product is purified or separated the methods of preparing chromatography.
According to embodiment of the present invention, the manufacturing method according to the foregoing shielding phenolic compounds of the present invention is further related to The shielding phenolic compounds of manufacture.
The shielding phenolic compounds of the present invention is due to showing excellent antioxygenic property, particularly suitable as antioxidant It uses, expects the biodiesel composition of excellent oxidation stability for manufacture especially as antioxidant.In consideration of it, according to An embodiment of the invention is related to a kind of biodiesel composition, and it includes any shielding phenolate conjunctions that the present invention is foregoing Object (or mixture of its arbitrary proportion) and underlying biological diesel oil.
Embodiment
The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.
Performance in embodiment and comparative example is evaluated as follows.
(1) oxidation stability is evaluated
The biodiesel composition manufactured using embodiment or comparative example is as test specimen, using EN14112：2003 methods Oxidation stability of (Racimat methods) determination sample at 110 DEG C, instrument are 743 type grease oxygen of Wan Tong companies of Switzerland Change stability meter.Oxidation induction period is longer, illustrates that the oxidation stability of biodiesel composition is better.
(2) cleansing performance is evaluated
Using the biodiesel that embodiment or comparative example manufacture as test specimen, using sheet metal sedimentation evaluation sample Cleansing performance.Instrument is the peace and quiet type analyzer of L-3 type derv fuels, and concrete operation method is：Clean deposit is received Storage is heated to 250 DEG C, with the flow velocity of 2mL/min by biodiesel composition constant flow to sediment trap, 50min Sediment trap is toasted at a high temperature of 180 DEG C afterwards, oxidation generation coast of paint film, then by the sediment trap just 2min is impregnated in heptane, then weigh be attached with deposit sediment trap weight, with clean sediment trap it Between difference again be sediment yield.Sediment yield is lower, illustrates that the cleansing performance of biodiesel composition is better.
Embodiment 1
In the 500ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 58.79g is added in (0.323mol) 2- tertiary butyl -6- mercapto-phenols, (alkylated reaction is catalyzed the boron trifluoride ether of 6.88g (0.048mol) Agent), polyisobutene (Mn=1000, the Jilin Chemical group fine chemicals of 100ml n-hexanes solvent and 161.61g (0.162mol) Co., Ltd manufactures), react 2h at 80 DEG C.After reaction, the potassium hydroxide solution cleaning reaction that use quality fraction is 5% Mixture once, and is washed to neutrality to remove catalyst with hot water, and then vacuum distillation removes solvent and unreacted phenol, obtains Obtain polyisobutene mercapto-phenol, hydroxyl value 53.49mgKOH/g.Hydroxy value measuring refers 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：It is polyisobutene at chemical shift 1.40 The characteristic peak of tertiary 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 integration for obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, it approaches Theoretical 1:1:1:1:1, it is analyzed from nuclear magnetic spectrogram, has synthesized the polyisobutene mercapto-phenol alkylation production of expected contraposition substitution Object.
Embodiment 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- methylphenols of addition, 9.29 grams of (112mmol) formaldehyde, 32.38 grams (176mmol) 4-aminodiphenylamine and 100mL toluene, it is rapid to stir, react 2h at 100 DEG C.It treats after reaction, decompression is steamed Solvent and a small amount of water of generation are removed in distillation, and pass through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.40 (9H), 2.37 (3H), 4.02 (1H), 4.83 (2H), 6.95-7.00 (12H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 21.2,30.1,34.1,49.9,114.3,118.9,119.4,121.8, 122.2,125.8,126.5,129.5,131.8,132.3,133.5,143.3,150.8；
C24H28N2OS calculated values C 73.43, H 7.19, N 7.14, O 4.08, S 8.17；Measured value：C 73.31, H 7.23, N 7.21, O 3.99, S 8.28.
Embodiment 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.86 grams of (62mmol) formaldehyde, 28.15 grams (153mmol) 4-aminodiphenylamine, 0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanols, it is rapid to stir, in 25 DEG C of reactions 24h.It treats after reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain shown in title The shielding phenol product of structure.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36-1.54 (18H), 3.75 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,51.2,119.4,121.8,126.5,129.5,131.4, 136.6,144.5,153.4；
C27H34N2OS calculated values C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Measured value：C 74.52, H 7.84, N 6.51, O 3.73, S 7.40.
Embodiment 4
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.24 grams of (15mmol) formaldehyde, 10.14 grams (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, it is rapid to stir, react 4h at 90 DEG C.It treats after reaction, vacuum distillation Solvent and a small amount of water of generation are removed, and passes through 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 (18H), 5.23 (2H), 6.80-7.02 (10H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.2,117.1,121.8,126.2,129.5,136.6, 143.6,153.4；
C33H38N2OS calculated values C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Measured value：C 77.71, H 7.52, N 5.53, O 3.10, S 6.23.
Embodiment 5
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.54 grams of (115mmol) formaldehyde, 18.49 grams (69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamines and 150mL benzene, it is rapid to stir, react 3h at 85 DEG C.It treats After reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain structure shown in title Shield phenol product.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H), 1.67 (2H), 3.47 (1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 17.9,22.4,29.6,34.6,45.2,52.7,58.6,119.4,121.8, 126.2,129.5,131.2,136.6,144.1,146.1,153.4；
C33H46N2OS calculated values:C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measured value：C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
Embodiment 6
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 3.57 grams of (15mmol) 2,6- di-t-butyl -4- mercapto-phenols, 5.14 grams of (62mmol) formaldehyde, 21.76 grams (103mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, it is rapid to stir, react 2h at 110 DEG C.It treats After reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain structure shown in title Shield phenol product.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (18H), 5.20 (2H), 5.32 (1H), 6.80-7.02 (14H), 7.17 (2H), 7.20 (1H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.5,117.1,120.4,126.2,129.5,132.3, 136.6,142.8,146.1,153.4；
C36H43N3OS calculated values C 77.83, H 7.20, N 6.98, O 2.66, S 5.33；Measured value：C 77.69, H 7.19, N 7.08, O 2.65, S 5.38.
Embodiment 7
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 34.51 grams of (145mmol) 2,6- di-t-butyl -4- mercapto-phenols, 2.91 grams of (35mmol) formaldehyde, 4.49 grams (21mmol) 4- amino -4'- methoxy diphenylamines, 0.26 gram of (2.61mmol) hydrochloric acid and 150mL benzene, it is rapid to stir, react 2h at 90 DEG C.It treats After reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain structure shown in title Shield phenol product.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (18H), 3.72-3.76 (4H), 4.80 (2H), 5.32 (1H), 6.97- 7.06 (8H), 7.17 (2H), 7.20 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,51.1,55.5,114.6,118.9,121.8,124.7, 126.5,132.3,136.6,144.5,153.4,154.5；
C28H36N2O2S calculated values C 72.38, H 7.81, N 6.03, O 6.89, S 6.90；Measured value：C 72.37, H 7.69, N 6.12, O 6.80, S 6.83.
Embodiment 8
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Addition gram 21.66 (91mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.35 grams of (9.51mmol) aldehyde C-9s, 6.51 grams (25mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene, it is rapid to stir, react 6h at 70 DEG C.It treats after reaction, to subtract Solvent and a small amount of water of generation is distilled off in pressure, and passes through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 0.88 (3H), 1.08-1.85 (24H), 5.23 (1H), 5.32 (1H), 6.80 (1H), 6.97 (8H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 14.1,22.6,29.6,31.7,34.6,41.6,60.8,116.6,119.4, 121.8,126.5,129.5,131.4,136.6,142.8,144.5,146.1,153.4；
C38H48N2OS calculated values C 78.57, H 8.33, N 4.82, O 2.75, S 5.52；Measured value：C 78.62, H 8.25, N 4.75, O 2.81, S 5.42.
Embodiment 9
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 8.33 grams of (35mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 4.23 grams of (51mmol) formaldehyde, 9.61 grams of (31mmol) N, N'- diphenyl -2,6- naphthylenediamine and 150mL toluene, it is rapid to stir, react 4h at 110 DEG C.It treats after reaction, vacuum distillation Solvent and a small amount of water of generation are removed, and passes through 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 (18H), 5.25 (2H), 5.32 (1H), 5.80 (1H), 6.99-7.06 (7H), 7.17 (3H), 7.26 (4H), 7.40 (2H), 7.84 (2H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,54.8,106.9,118.6,123.3,126.2,129.2, 136.6,142.8,148.3,153.5；
C37H41N2OS calculated values C 79.24, H 7.19, N 5.00, O 2.85, S 5.72；Measured value：C 79.20, H 7.23, N 5.14, O 2.72, S 5.65.
Embodiment 10
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 6.19 grams of (26mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.57 grams of (92mmol) 3- methylthiopropionaldehyde aldehyde, 3.13 grams (17mmol) 4-aminodiphenylamine and 150mL toluene, it is rapid to stir, react 2h at 80 DEG C.It treats after reaction, vacuum distillation Solvent and a small amount of water of generation are removed, and passes through 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 1.36-1.54 (18H), 2.12-2.80 (7H), 3.47 (1H), 4.97 (1H), 5.32 (1H), 6.97 (7H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 15.2,29.6,31.9,34.6,41.7,60.2,114.3,119.4,121.8, 126.2,129.5,132.4,136.6,144.5,146.1,153.5；
C30H40N2OS2Calculated value C 70.82, H 7.92, N 5.51, O 3.14, S 12.60；Measured value：C 70.75, H 7.83, N 5.46, O 3.20, S 12.71.
Embodiment 11
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols, 4.4 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) N- Diphenyl-para-phenylene diamine and 150mL ethyl alcohol, it is rapid to stir, after 60 DEG C are reacted 2.5h, room temperature is down to, is added in 7.05 grams (85mmol) Formaldehyde is warming up to 85 DEG C of reaction 2.5h.It treats after reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column Chromatography obtains the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (18H), 3.74 (1H), 4.12 (2H), 4.59 (1H), 4.83 (2H), 5.32 (1H), 6.97-7.11 (5H), 7.17 (2H), 7.24 (2H)；
13C NMR (75MHz, CDCl3)：δ 29.6,33.1,34.6,50.6,119.4,123.3,126.2,126.7, 127.9,136.6,140.5,142.9,153.4；
C26H34N2OS calculated values C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Measured value：C 75.20, H 7.59, N 6.29, O 3.65, S 7.22.
Embodiment 12
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.04 grams of (121mmol) formaldehyde, 19.93 grams (94mmol) 4- amino -4'- ethyls diphenylamines and 150mL dimethylbenzene, it is rapid to stir, after 90 DEG C are reacted 3h, room temperature is down to, is added Enter 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine, be warming up to 150 DEG C of reaction 8h.It treats after reaction, decompression Solvent and a small amount of water of generation is distilled off, and passes through 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 1.23 (1H), 1.36 (18H), 2.61 (2H), 3.77 (1H), 4.84 (2H), 5.32 (1H), 5.70 (1H), 6.98 (5H), 7.17 (2H), 7.49 (1H)；
13C NMR (75MHz, CDCl3)：δ 15.60,29.6,34.6,50.7,118.9,121.8,126.2,129.7, 136.6,141.2,146.1,153.4；
C29H36N2OS2Calculated value C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Measured value：C 70.77, H 7.41, N 5.67, O 3.17, S 12.93.
Embodiment 13
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 10.95 grams of (46mmol) 2,6- di-t-butyl -4- mercapto-phenols, 3.98 grams of (48mmol) formaldehyde, 13.78 grams (53mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL trimethylbenzenes, it is rapid to stir, after 85 DEG C are reacted 1h, add in 3.82 grams (46mmol) formaldehyde continues after 85 DEG C are reacted 1h, is down to room temperature, adds in 10.11 grams of (316mmol) sulphur and 0.27 gram (2.11mmol) iodine is warming up to 180 DEG C of reaction 1h.It treats after reaction, vacuum distillation removes solvent and a small amount of water of generation, and The shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (18H), 4.26 (2H), 5.18 (2H), 5.32 (1H), 6.40 (1H), 6.97 (8H), 7.17 (2H), 7.37 (2H)；
13C NMR (75MHz, CDCl3)：δ 29.6,33.6,34.6,54.3,106.5,114.4,119.4,121.8, 126.2,129.5,136.6,141.9,144.5,153.4；
C34H36N2OS2Calculated value C 73.87, H 6.56, N 5.07, O 2.89, S 11.60；Measured value：C 73.91, H 6.49, N 5.02, O 2.94, S 11.49.
Embodiment 14
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols, 7.39 grams of (89mmol) formaldehyde, 6.62 grams (36mmol) 4-aminodiphenylamine, 0.45 gram of (4.51mmol) sodium hydroxide and 150mL isopropanols, it is rapid to stir, react 3h at 80 DEG C.It treats After reaction, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain structure shown in title Shield phenol product.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36-1.54 (36H), 4.82 (4H), 5.32 (2H), 6.97 (7H), 7.17 (4H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,56.5,106.5,119.4,121.8,126.5,129.5, 131.4,136.6,144.5,146.1,153.4；
C42H56N2O2S2Calculated value C 73.64, H 8.24, N 4.09, O 4.67, S 9.36；Measured value：C 73.59, H 8.21, N 4.15, O 4.62, S 9.34.
Embodiment 15
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 6.55 grams of (36mmol) 2- tertiary butyl -4- mercapto-phenols, 7.64 grams of (92mmol) formaldehyde, 13.06 grams of (71mmol) N- benzene Base p-phenylenediamine and 150mL toluene, it is rapid to stir, react 4h at 90 DEG C.It treats after reaction, vacuum distillation removes solvent and life Into a small amount of water, and pass through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (9H), 3.81 (1H), 4.38 (2H), 4.69 (2H), 5.29 (1H), 6.95-7.00 (15H), 7.17 (1H), 7.26 (4H), 7.55 (1H), 8.62 (1H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,43.5,50.8,114.3,119.4,121.8,125.4, 129.5,132.3,136.6,145.2,146.1,149.0,153.4；
C36H38N4OS calculated values C 75.23, H 6.66, N 9.75, O 2.78, S 5.58；Measured value：C 75.27, H 6.69, N 9.68, O 2.79, S 5.51.
Embodiment 16
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 11.66 grams of (49mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.92 grams of (53mmol) 2,6- DI-tert-butylphenol compounds, 7.89 grams of (95mmol) formaldehyde, 11.23 grams of (32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, it is rapid to stir, react 3h at 100 DEG C.It treats after reaction, vacuum distillation removes solvent and a small amount of water of generation, And pass through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36-1.54 (36H), 4.91 (2H), 5.22 (2H), 5.32 (2H), 6.97- 7.07 (16H), 7.17 (2H), 7.20 (1H), 7.27 (4H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.4,55.6,56.9,93.6,119.4,123.3,126.5, 129.2,131.4,136.6,142.8,146.1,153.4；
C54H65N3O2S calculated values C 79.08, H 7.99, N 5.12, O 3.90, S 3.91；Measured value：C 79.15, H 8.03, N 5.01, O 3.87, S 3.85.
Embodiment 17
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 47.16 grams of (45mmol) polyisobutene mercapto-phenols (embodiment 1 manufactures) of addition, 4.23 grams of (51mmol) formaldehyde, 9.75 grams (53mmol) 4-aminodiphenylamine and 150mL benzene, it is rapid to stir, react 2.5h at 80 DEG C.It treats after reaction, vacuum distillation Solvent and a small amount of water of generation are removed, and passes through 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 0.88,0.98,1.02,1.24,1.40,2.42,4.86,6.97,7.02, 7.14,7.26,7.55；
13C NMR (75MHz, CDCl3)：δ 28.2,30.1,32.3,34.5,38.1,49.8,59.1,114.3,119.4, 121.8,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Embodiment 18
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 29.34 grams of (28mmol) polyisobutene mercapto-phenols (embodiment 1 manufactures) of addition, 2.91 grams of (35mmol) formaldehyde, 6.24 grams (24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, it is rapid to stir, react 2h at 90 DEG C.It treats after reaction, Vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 0.88,0.98,1.02,1.24,1.40,2.42,4.00,4.86,5.56, 6.97,7.02,7.14,7.26,7.55；
13C NMR (75MHz, CDCl3)：δ 28.2,30.1,32.3,33.1,34.5,38.1,49.8,59.1,114.3, 119.4,121.8,125.2,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Comparative example 1
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols, 7.22 grams of (87mmol) formaldehyde, 14.37 grams (85mmol) Diphenylamines and 150mL methanol, it is rapid to stir, react 2h at 60 DEG C.It treats after reaction, vacuum distillation removes solvent and generation A small amount of water, and pass through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H), 7.27(4H)；
13C NMR (75MHz, CDCl3)：δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2, 136.6,150.0,153.5；
C27H33NOS calculated values C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measured value：C 77.22, H 7.89, N 3.31, O 3.83, S 7.67.
Comparative example 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, Add in 10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamines and 150mL methanol, it is rapid to stir, react 4h at 70 DEG C.Treat reaction knot Shu Hou, vacuum distillation removes solvent and a small amount of water of generation, and passes through column chromatography for separation and obtain the shielding phenol of structure shown in title Product.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H), 4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 17.9,22.40,24.6,30.4,34.3,45.7,54.5,56.7,116.6, 120.4,121.8,125.9,128.9,129.5,135.6,146.1,153.5,154.8；
C33H46N2O calculated values C 81.43, H 9.53, N 5.76, O 3.29；Measured value：C 81.38, H 9.51, N 5.79, O 3.31.
Comparative example 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flasks equipped with blender, thermometer, condenser pipe and dropping funel, 9.24 grams of (33mmol) 2,6- di-t-butyls -4- (3- mercaptopropyis) phenol of addition, 3.07 grams of (37mmol) formaldehyde, 11.71 grams (45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene, it is rapid to stir, react 4h at 80 DEG C.It treats after reaction, to subtract Solvent and a small amount of water of generation is distilled off in pressure, and passes through column chromatography for separation and obtain the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows：
1H NMR (300MHz, CDCl3)：δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32 (1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3)：δ 28.7,31.1,34.3,35.7,54.1,117.1,119.4,123.3, 124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS calculated values C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measured value：C 78.27, H 7.96, N 4.98, O 2.92, S 5.83.
Comparative example 4~7
The composition of the comparative example 4~7 of antioxidant is shown in Table 1.
Table 1
The embodiment 19~28 of biodiesel, the formula composition of comparative example 8~14 and oxidation stability experiment and lubrication Property experiment test result be shown in Table 2.
Table 2
From table 2 it can be seen that biodiesel composition of the present invention have excellent oxidation stability and cleansing performance and The stronger ability for inhibiting deposit generation.

Claims (19)

1. a kind of biodiesel composition, including shielding phenolic compounds and major amount of underlying biological diesel oil, the shielding phenolate Close object structure be：
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Straight or branched alkyl, general formula (II) group shown in group and logical formula (III) shown in, on condition that at least one group R is the group shown in logical formula (II)； Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl,
In foregoing each logical formula (II), (III) and (IV), each group L is same or different to each other, and is group independentlyWherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branch chain miscellaneous alkyl；Each group R2It is mutually the same Or it is different, it is each independently selected from hydrogen, C1-20Shown in group and logical formula (V) shown in straight or branched alkyl, logical formula (IV) Group；Each group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Straight or branched alkyl；Each group RcEach other It is identical or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup；Y is 0 to 3 Integer；Z is 0 to 3 integer；N is 1 to 8 integer；N' is 0 to 7 integer, on condition that n'+n≤8；Each group RdEach other It is identical or different, it is each independently selected from hydrogen and the group shown in logical formula (V)；Each cyclic groupIt is mutually the same or not Together, phenyl ring and naphthalene nucleus are each independently selected from, wherein two adjacent cyclic groupsEach other optionally by additional S atom and bridge the two rings N atoms and formed phenthazine ring and/or, adjacent two cyclic groupsEach other Optionally pass through additional groupWith bridge the two rings N atoms and form 9,10- acridan rings,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Straight or branched alkyl, general formula (II) group shown in group and logical formula (III) shown in；Each group R' is same or different to each other, be each independently selected from hydrogen and C1-20Straight or branched alkyl；Group L is groupA be 0 or 1, and two group R and a group- (S)a- L- occupies three positions of residue on phenyl ring respectively,
Wherein, the linear chain or branch chain miscellaneous alkyl be selected from straight or branched alkyl molecular structure inside one or more groups- CH2- the group and straight or branched alkyl for directly being substituted and obtained by the substituting group selected from one of-O- ,-S- and-NR'- point One or more group-CH inside minor structure<By substituting group-N<The group for directly substituting and obtaining, wherein the shielding phenol Compound at least one group R in its entire molecular structuredIt is hydrogen.
2. biodiesel composition described in accordance with the claim 1, which is characterized in that
Each group R is each independently selected from hydrogen, C1-10Straight or branched alkyl or the polyene that number-average molecular weight Mn is 300-3000 Group shown in alkyl, logical formula (II) and the group shown in logical formula (III)；Each group R' is each independently selected from hydrogen and C1-4Directly Chain or branched alkyl；
Group R " is selected from hydrogen, C1-20Straight or branched alkyl and C3-20Linear chain or branch chain miscellaneous alkyl；Each group R2It selects independently From hydrogen, C1-10Group shown in straight or branched alkyl and logical formula (IV)；Each group RbIt is each independently selected from hydrogen and C1-10Straight chain Or branched alkyl；Each group RcIt is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl oxygen Base；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0,1 or 2, on condition that n'+n=1 or n'+n=2；Each group RdFor hydrogen；Respectively Cyclic groupSelected from phenyl ring.
3. biodiesel composition described in accordance with the claim 2, which is characterized in that group R " is selected from hydrogen, C1-10Linear chain or branch chain Alkyl and C3-10Linear chain or branch chain miscellaneous alkyl.
4. biodiesel composition described in accordance with the claim 2, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
5. biodiesel composition described in accordance with the claim 1, which is characterized in that each group R be each independently selected from hydrogen and C1-300Straight or branched alkyl.
6. biodiesel composition described in accordance with the claim 1, which is characterized in that the shielding phenolic compounds is selected from following The mixture of particular compound or its arbitrary proportion：
7. a kind of biodiesel composition, including shielding phenolic compounds and major amount of underlying biological diesel oil, the shielding phenolate Closing the manufacturing method of object includes making the phenolic compounds shown in logical formula (X) and the amine compounds shown in general formula (Y) shown in general formula (Z) Aldehyde compound in the presence of the first step that reacts, optionally further include the reaction product for making the first step and vulcanization Agent is reacted and/or the additional step with the aldehyde compound reaction shown in general formula (Z),
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branch chain alkane Base, on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight chain Or branched alkyl,
In general formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group Rb It is same or different to each other, is each independently selected from hydrogen and C1-20Straight or branched alkyl；Each group RcIt is same or different to each other, respectively From independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl oxygroup；Y is 0 to 3 integer；Z be 0 to 3 integer；N1 is 1 to 8 integer；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and Naphthalene nucleus,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branch chain miscellaneous alkyl,
Wherein, the linear chain or branch chain miscellaneous alkyl be selected from straight or branched alkyl molecular structure inside one or more groups- CH2- the group and straight or branched alkyl for directly being substituted and obtained by the substituting group selected from one of-O- ,-S- and-NR'- point One or more group-CH inside minor structure<By substituting group-N<The group for directly substituting and obtaining.
8. according to the biodiesel composition described in claim 7, which is characterized in that the aldehyde compound shown in general formula (Z) is first Aldehyde；The vulcanizing agent is sulphur；
Each group R0It is each independently selected from hydrogen ,-SH and C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000 It is polyolefin-based；Each group R' is each independently selected from hydrogen and C1-4Straight or branched alkyl；
Each group RbIt is each independently selected from hydrogen and C1-10Straight or branched alkyl；Each group RcIt is each independently selected from hydrogen, C1-10 Straight or branched alkyl and C1-10Straight or branched alkyl oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic groupSelected from phenyl ring；Group R " is selected from hydrogen, C1-20Straight or branched alkyl and C3-20Linear chain or branch chain miscellaneous alkyl.
9. according to the biodiesel composition described in claim 8, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
10. according to the biodiesel composition described in claim 8, which is characterized in that group R " is selected from hydrogen, C1-10Straight chain or branch Alkyl group and C3-10Linear chain or branch chain miscellaneous alkyl.
11. according to the biodiesel composition described in claim 7, which is characterized in that in the first step, the general formula (X) molar ratio of the phenolic compounds shown in and the amine compounds shown in the general formula (Y) is 1:0.1-10, the logical formula (X) institute The molar ratio of the phenolic compounds shown and the aldehyde compound shown in the general formula (Z) is 1:0.1-10, in the additional step, institute The molar ratio for stating the amine compounds shown in general formula (Y) and the vulcanizing agent is 1:1-10, the amine compounds shown in the general formula (Y) Molar ratio with the aldehyde compound shown in the general formula (Z) is 1:0.1-10.
12. according to the biodiesel composition described in claim 7, which is characterized in that in the first step, the general formula (X) molar ratio of the phenolic compounds shown in and the amine compounds shown in the general formula (Y) is 1:0.5-5.0, the logical formula (X) institute The molar ratio of the phenolic compounds shown and the aldehyde compound shown in the general formula (Z) is 1:0.5-5.0, in the additional step, The molar ratio of amine compounds and the vulcanizing agent shown in the general formula (Y) is 1:1.2-6.0, the amine shown in the general formula (Y) Compound and the molar ratio of the aldehyde compound shown in the general formula (Z) are 1:0.5-5.0.
13. according to the biodiesel composition described in claim 7, which is characterized in that in the first step, the general formula (X) molar ratio of the phenolic compounds shown in and the amine compounds shown in the general formula (Y) is 1:0.8-2.0, the logical formula (X) institute The molar ratio of the phenolic compounds shown and the aldehyde compound shown in the general formula (Z) is 1:0.8-2.0, in the additional step, The molar ratio of amine compounds and the vulcanizing agent shown in the general formula (Y) is 1:1.5-3.0, the amine shown in the general formula (Y) Compound and the molar ratio of the aldehyde compound shown in the general formula (Z) are 1:0.8-2.0.
14. according to the biodiesel composition described in one of claim 1-13, which is characterized in that the shielding phenolic compounds exists Content is 10~50000mg/kg in the biodiesel composition；The underlying biological diesel oil is fatty acid ester of low-carbon alcohol.
15. according to the biodiesel composition described in one of claim 1-13, which is characterized in that the biodiesel composition In contain selected from petroleum diesel, Fiscber-Tropscb synthesis diesel oil, the one kind being hydrocracked in biodiesel and oxygen-containing diesel oil blending component or It is a variety of.
16. according to the biodiesel composition described in one of claim 1-13, which is characterized in that the shielding phenolic compounds exists Content is 20~10000mg/kg in the biodiesel composition.
17. according to the biodiesel composition described in one of claim 1-13, which is characterized in that the shielding phenolic compounds exists Content is 30~5000mg/kg in the biodiesel composition.
18. according to the biodiesel composition described in one of claim 1-13, which is characterized in that combined in the biodiesel Antioxidant, cetane improver, detersive, dispersant, pour-point depressant, viscosity index improver, metal deactivator, anti-is added in object One or more in rust agent and anti-foaming agent.
19. the manufacturing method of the biodiesel composition described in one of claim 1-13, including making the shielding phenol and described The step of underlying biological diesel oil mixes.
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