CN105732537B - Bifunctional compound containing hindered phenol and crown ether structure, synthetic method and application thereof - Google Patents

Abstract

The compound containing antistatic and antioxidant double functional groups consists of hindered phenol unit, crown ether unit and straight chain segment unit. The effective content of functional groups in the unit mass of the compound and the compatibility of the compound with the resin are adjusted by controlling the length of the linear chain segment unit. The hindered phenol structural unit can be transferred to the surface layer of the resin through the transfer function of the crown ether group, so that the oxidation in the air can be more effectively eliminated; the hindered phenol unit can effectively prevent the crown ether structure from falling off from the surface of the resin due to a larger space structure, and the antistatic time of the compound is prolonged. The compound of the invention can be used as an antistatic antioxidant for polypropylene or polyethylene.

Description

A kind of dual-function compound comprising hindered phenol and crown ether structures, synthetic method and its Using

Technical field

The present invention relates in a kind of anti-oxidant antistatic dual-function compound and its synthetic method more particularly to a kind of molecule Include the compound and its synthetic method of hindered phenol group and crown ether structures hydrophilic radical simultaneously, the invention further relates to the compounds Application in vistanex.

Background technology

Hindered phenol compound passes through hydrogen atom due to that can fight for the peroxy radical formed in autoxidation with polymer Transfer, formed carboxylic acid and a kind of stabilization antioxidant free radical, the free radical again have capture living radical ability, can With the second kinetic chain of the polymer chain type oxidation reaction that terminates.Hinered phenols antioxidant typically passes through ester under alkaline condition The mode of exchange generates.Such as：US4716244, US5481023, US5563291, US6878843, US2003166962 are described It is catalyst preparation Hinered phenols antioxidant with lithium amide, lithium acetate, sodium acetate, magnesium acetate, three b propanol aluminium, zinc acetate etc. The process of (such as antioxidant 1010,1076,245 and 1135).

Amphiphilic compound can occur to migrate and move to resin surface and form dense arrangement in resin, and surface is dense Degree forms conductive layer higher than inside, hydrophilic unit towards air, in conjunction with the moisture in air so that the electrostatic charge of accumulation is dissipated Ease, the effective aggregation for reducing deleterious charge.Amphiphilic macromolecular compound antistatic agent is typically that polycondensation reaction is made.Such as： CN200810046009.0, CN200810150057.4, CN02151546.8 describe the amphiphilic anti-quiet of different molecular structures The preparation process of electric agent.

Hinered phenols antioxidant and parents' class antistatic agent are widely used in polyolefin products at this stage, Hinered phenols antioxygen Agent is relatively uniform to be dispersed among resin and plays antioxidation, but it only has surface to be contacted therefore with air after resin forming Only a small amount of Hinered phenols molecule plays antioxidation, thus greatly reduces antioxidant effect.

Parents' class compound can occur to migrate and move to the surface of resin in resin, therefore, when in same molecule When not only having contained hindered phenol structure but also having contained amphiphilic structure, it can be transported to the surface of resin with the entire molecule of migration of amphiphilic structure Dynamic, hindered phenol structure increases in the content of resin surface at this time, and antioxidant effect is remarkably reinforced.

Invention content

The purpose of the present invention is exactly to overcome shortcoming existing for the above-mentioned antioxidant effect of antioxidant in the prior art And provide a kind of compound and its synthetic method of the double-functional group comprising hindered phenol structure and amphiphilic structure of function admirable.

Under the structure such as formula (I) of compound provided by the present invention：

Wherein n is the positive integer of 3-16；M is the positive integer of 6-12.

The purpose of the present invention can be achieved through the following technical solutions：

Used raw material includes：2,6- di-tert-butyl methyl phenols, dimethyl suflfate, N- bromo-succinimides, It is azodiisobutyronitrile, straight diol, straight chain dibromoalkane, Boron tribromide diethyl ether solution, triethylene-glycol, ethylene oxide, right Toluenesulfonamide, paratoluensulfonyl chloride and metallic sodium etc..

1st step, the protection of phenolic hydroxyl group：

Reactor is added in 2,6-di-tert-butyl p-methylphenol and dimethyl suflfate, is in molar ratio 2,6- di-t-butyls P-methyl phenol: dimethyl suflfate=1: (1.1~2), while reaction solvent A is added, and under nitrogen protection, reaction temperature 45 DEG C~61 DEG C, the reaction time is 0.1h~2h, generates 2,6- di-t-butyl p-methyl anisoles；

Phenolic hydroxyl group protection reaction process be：

In phenolic hydroxyl group protects reaction process, nuclear magnetic resonance spectroscopy is used¹Bis- tertiary fourths of 2,6- in H NMR analysis monitoring reactants The content of base p-methyl phenol, until inspection does not measure 2,6-di-tert-butyl p-methylphenol in reactant；It usually can be every 10 Minute monitoring is primary, and unequal interval cycle monitoring can also be used.

By theoretical value, dimethyl suflfate should be the half of 2,6-di-tert-butyl p-methylphenol, when practical application, add The dimethyl suflfate entered is obviously excessive, to ensure the total overall reaction of 2,6-di-tert-butyl p-methylphenol.Nitrogen rises in reaction To the protective effect to reaction, prevent oxygen or other impurities for the interference of reaction.

Reaction solution is cooled to room temperature after the reaction was complete, dilute potassium carbonate solution is added into reaction solution and is extracted, it is organic It is mutually evaporated after drying and can be obtained pure 2,6- di-t-butyl p-methyl anisoles.

2nd step, the α bromos of 2,6- di-t-butyl p-methyl anisoles：

Reactor is added in 2,6- di-t-butyls p-methyl anisole and N- bromo-succinimides, is in molar ratio 2,6- Di-t-butyl p-methyl anisole: bromo-succinimide=1 N-: (1~1.5), while reaction dissolvent B is added, it is protected in nitrogen Under shield, under the catalytic action of azodiisobutyronitrile, 50 DEG C~77 DEG C of reaction temperature, 2~5 hours reaction time generates 2,6- Di-t-butyl is to bromomethyl methyl phenyl ethers anisole.

The equation of bromo-reaction is：

During bromo-reaction, the color of observing response solution when the orange color dissipated of reaction solution, and has white precipitate generation The reaction was continued afterwards 1~2 hour.

Intermediate product 2 in the present invention, the method that 6- di-t-butyls can use recrystallization to the purification of bromomethyl methyl phenyl ethers anisole are selected The solvent of recrystallization is n-hexane.

3rd step, alcoholization reaction of 2, the 6- di-t-butyls to bromomethyl methyl phenyl ethers anisole：

By 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole and glycol compound HO (CH₂)_nOH be added reactor, by mole Than being 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole: diol compound=1: (1.1~3) are added with 2,6- di-t-butyls to bromine The alkaline matter of methylanisole equimolar amounts, this alkaline matter can be：Sodium hydroxide, potassium hydroxide, potassium carbonate, carbonic acid Sodium.Reaction dissolvent C is added simultaneously, under the catalytic action of alkaline matter, reaction solution is heated to flowing back, 5 hours reaction time ~60 hours, generate 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole.

The equation of bromo-reaction is：

Diol compound HO (CH used in reaction₂)_nThe positive integer that n is 3~16 in OH.

The shift value of thin-layer chromatography when reaction using reactants and products on silica gel plate is different, solvent be chloroform, Methanol, monitoring 2,6- di-t-butyls are gradually thin out until no longer changing to the colour developing point of bromomethyl methyl phenyl ethers anisole, stop heating, It is extracted distilled water is added into reaction solution after reaction solution recovery room temperature, after being dried to organic phase, utilizes column chromatography for separation Obtain clean product.

4th step, the bromination reaction of 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole：

Upper step is reacted into 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole and straight chain dibromoalkane obtained Reactor is added, is the ︰ 3 of 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) Ben Jia Mi ︰ dibromoalkanes=1 according to molar ratio ~5, the alkaline matter with 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole equimolar amounts, this alkalinity is added Substance can be：Sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate.Reaction dissolvent D is added simultaneously, reaction solution is heated to reflux 10~48 hours, heat filtering removed insoluble impurities, and vacuum distillation removes solvent and obtains solid crude product, utilized column chromatography point afterwards From obtaining clean product [(3,5- di-t-butyls, 4- methoxyl groups) tolyl, m- bromine m alkyl] 1, n-n diether.

Bromo-derivative prepare reaction equation be：

Wherein n is the positive integer of 3-16；M is the positive integer of 6-12.

Reaction process is monitored using thin-layer chromatography, is no longer changed when the colour developing point of third step reaction product is progressively reduced until After continue heating 1-2 hour after stop react.The method for being evaporated under reduced pressure obtained solid crude product column chromatography carries out separation and carries It is pure.

5th step, the deprotection reaction of hydroxyl：

Reactor is added in the bromo-derivative of 4th step reaction gained and Boron tribromide, is in molar ratio bromo-derivative: Boron tribromide =3: 1~3, the Boron tribromide for reacting used is the diethyl ether solution of Boron tribromide；Reaction dissolvent E is added simultaneously, upper step is reacted Products therefrom is added among the three-necked flask containing dichloromethane, will be molten in advance after reacting liquid temperature is down to 0 DEG C~-50 DEG C Among solution has the dichloromethane solution of Boron tribromide to be slowly added into flask with dropping funel, time for adding is 1~5 hour.Drop It is stirred 2~5 hours after reaction solution is restored to room temperature after adding.

Hydroxyl deprotection reaction equation be：

Using thin-layer chromatography monitor reaction process, when the 4th step reaction gained bromide colour developing point taper into until Stop reaction after disappearance.Reaction solution is transferred in separatory funnel, distilled water of the pH value between 7~8 is added, after extracting repeatedly It is dried 6~24 hours with anhydrous magnesium sulfate after organic layer is separated, will be evaporated to obtain under filter vacuum after being filtered to remove drier Clean product [(3,5- di-t-butyls, 4- hydroxyls) tolyl, m- bromine m alkyl] 1, n-n diether.

6th step, the preparation of Chloramine

Metallic sodium is cut into stirring and dissolving concentration in silk input solvent F to be cooled to room temperature, be added in 0.01~0.03g/ml With the toluene 4- sulfonamide of metallic sodium molar ratio 0.5~2,1~6h postcoolings are heated to reflux to room temperature, filtering is drenched with solvent F It washes, is dried to obtain white solid product toluenesulfonamide sodium.

The reaction equation of the preparation of toluenesulfonamide sodium is

Reaction process is monitored using thin-layer chromatography, is stopped after the colour developing point of toluenesulfonamide tapers into until disappearing anti- It answers.It will be filtered after reaction solution postcooling to room temperature, solid product is eluted with solvent F, is dried to obtain white solid product toluene sulphur Amide sodium

7th step, the sulfonylation of triethylene-glycol

Triethylene-glycol is dissolved in solvent G in flask, controlled concentration be 0.25~0.4g/ml, then be added with The sodium hydrate aqueous solution that triethylene-glycol molar ratio is 2~4, a concentration of 0.15~0.3g/ml of sodium hydrate aqueous solution are used Ice-water bath is cooled to 0~5 DEG C, and the G solution for the paratoluensulfonyl chloride for being 1.5~3 with triethylene-glycol molar ratio is slowly added dropwise, It is added dropwise, keeps the temperature at 0~5 DEG C and continue to be stirred to react 1~5h, stop reaction, pour the mixture into ice water and stir, A large amount of white solids are precipitated, filter, wash, it is dry, it is recrystallized to give white product with solvent H；

Reaction process is monitored using thin-layer chromatography, is stopped after the colour developing point of first triethylene-glycol tapers into until disappearing Only react.Crude product is recrystallized to give white double p-methylbenzoic acid Triethylene Glycol products with solvent H.

8th step, the annulation of triethylene-glycol

The obtained compound of 6th step is added in solvent I and is heated with stirring to 60~100 DEG C, is cooled to room temperature, into system It is 3~1 to be added with the 6th step product molar ratio:60~100 DEG C of reactions 5 of the obtained compound agitating and heating of 1 the 7th step and holding~ 20h is depressurized and is steamed solvent I, mixed solution 0.5~1h of stirring of addition methanol and water, and the volumetric concentration ratio of methanol and water is (30~70) ︰ (70~30) are added 60~100 DEG C of distilled water and stir 0.5~1h, add a concentration of 1~5mol/L 60~ 100 DEG C of sodium hydroxide solution stirring, obtains Off-white solid, filters, dry, and white product is recrystallized to obtain with solvent I.

The equation of annulation

Reaction process is monitored using thin-layer chromatography, is stopped after the colour developing point of the 7th step product tapers into until disappearing anti- It answers.Crude product is recrystallized to give white N with solvent M, and N- bis- is to 6 product of -18 crown- of methyl benzoyl -1,10- diaza.

9th step, the preparation of -18 crown- 6 of 1,10- diaza

Under nitrogen protection, lithium aluminium hydride (2.28g, 60mmo1) is added in three-neck flask dense in 40mL solvents J Degree is 35~80g/L, is stirred evenly, and the molar ratio for being slowly added to the 8th step reaction product and lithium aluminium hydride is 0.02~0.1, is added Heat 60~90h of reflux, restores to room temperature, and the aqueous solution of solvent J is added, and filtering is spin-dried for, and precipitating solvent K recrystallizations obtain white Color product.

Reaction process is monitored using thin-layer chromatography, is stopped after the colour developing point of the 8th step product tapers into until disappearing anti- It answers.Crude product is recrystallized to give white product with solvent K.

10th step, the preparation of crown ether glycol

Under nitrogen gas shielded, by -18 crown- 6 of 1,10- diazas and ethylene oxide in molar ratio 1 in round-bottomed flask:1 ~3 mixing are added solvent M and are heated to reflux 2~for 24 hours, are cooled to room temperature, and decompression steams solvent, are recrystallized to give white crystal production - 18 crown- 6 of object N, N- diethyl alcohol radical -1,10- diaza.

Reaction process is monitored using thin-layer chromatography, is stopped after the colour developing point of the 9th step product tapers into until disappearing anti- It answers.Crude product is recrystallized to give white product with solvent N.

11st step, the preparation of hindered phenol-crown ether Amphi-pathic compound

5th step is reacted bromo-derivative obtained to press with N, -18 crown- 6 of N- diethyl alcohol radicals -1,10- diaza made from upper step Molar ratio 3~1:3 mixing, while addition and the equimolar alkaline matter of bromo-derivative, this alkaline matter can be：Hydroxide Sodium, potassium hydroxide, potassium carbonate, sodium carbonate.Reaction dissolvent N is added simultaneously, reaction solution is heated to reflux 10-48 hours, heat filtering Insoluble impurities is removed, vacuum distillation removes solvent and obtains solid crude product, obtains clean product N using column chromatography for separation afterwards, N- bis- { [(3,5- di-t-butyls, 4- hydroxyls) tolyl, m-m alkyl] 1, n-n glycol ether-ethyl } -1,10- diazas -18 Crown- 6.

Wherein n is the positive integer of 3-16；M is the positive integer of 6-12.

Reaction process is monitored using thin-layer chromatography, is no longer changed when the colour developing point of the 10th step reaction product is progressively reduced until After continue heating 1-2 hour after stop react.The method for being evaporated under reduced pressure obtained solid crude product column chromatography carries out separation and carries It is pure.

Involved synthesis step is conventional methodology of organic synthesis in above technical scheme, is reacted used by each step Solvent is the Conventional solvents for being suitble to such synthetic reaction, and those skilled in the art can be into according to the professional knowledge and common sense of grasp Row conventional selection is not specially limited in of the invention.In order to reach better reaction effect, the present invention provides reaction solvent A-N Preferred embodiment.Preferred embodiment is：

A solvents are selected from following at least one：Chlorobenzene, dichloromethane, chloroform, toluene；

B solvents are selected from least one of following：Benzene, dichloromethane, chloroform, carbon tetrachloride；

C solvents are selected from least one of following：Methanol, ethyl alcohol, acetone, dimethylformamide；

D is selected from least one of following：Triethylamine, ethyl alcohol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, two Chloromethanes, carbon tetrachloride, ethyl acetate；

F solvents are selected from following at least one：Ethyl alcohol, methanol, chloroform, dichloromethane；

E is selected from least one of following：Dichloromethane, chloroform, carbon tetrachloride；

G solvent is selected from least one of following：Tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride；

H solvents are selected from least one of following：Methanol, ethyl alcohol, acetone, dimethylformamide；

I is selected from least one of following：Dimethyl sulfoxide (DMSO), dimethylformamide, tetrahydrofuran, acetonitrile；

J is selected from least one of following：Tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride；

K solvents are selected from following at least one：N-hexane, dichloromethane, chloroform, toluene；

M solvents are selected from least one of following：Ethyl alcohol, methanol, chloroform, dichloromethane；

N solvents are selected from least one of following：Triethylamine, ethyl alcohol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorine Benzene, dichloromethane, carbon tetrachloride, ethyl acetate.

The compound that the present invention synthesizes can be used as the antioxidant of polypropylene or polyethylene and antistatic agent uses.According to system Such compound is added to according to mass content 0.01% to 1% in polypropylene or polyethylene base-material by the different purposes of product, warp Anti-oxidant and antistatic effectiveness can be played after extruder grain.

Using chemically synthesized method, hindered phenol structure unit and crown ether structures list are introduced simultaneously in the same molecule Member.Hindered phenol structure passes through the transfer of hydrogen atom, shape due to that can fight for the peroxy radical formed in autoxidation with polymer At the antioxidant free radical of carboxylic acid and a kind of stabilization, which has the ability of capture living radical again, can terminate poly- The second kinetic chain of object chain type oxidation reaction is closed, therefore hindered phenol structure unit is deposited as the anti-oxidant functional group of entire molecule .Crown ether structures are a kind of typical hydrophilic lipophobic structures, when the compound containing crown ether structures is added in macromolecule resin, Since the compound that hydrophilic lipophobic interaction contains crown ether structures can be to macromolecule resin surface migration, the chemical combination containing crown ether structures Object contacts the moisture film to be formed and can guide charge with the water in air on macromolecule resin surface, to prevent macromolecule resin surface electricity Lotus is accumulated, therefore crown ether structures unit can be used as the antistatic functional group use of entire molecule.When both having contained in the same molecule Hindered phenol structure unit contains crown ether structures unit again when, two kinds of structural units are original anti-oxidant and antistatic except each self-sustaining Function except, due to crown ether structures unit because hydrophilic lipophobic interaction to macromolecule resin surface migration can drive hindered phenol simultaneously Structural unit is moved to resin surface inside resin and is enriched in resin surface, improves resin surface hindered phenol structure unit Quantity, the antioxidation of reinforced resin, thus preferably protect macromolecule resin product from the hot oxygen environment in air It influences.Simultaneously because hindered phenol structure unit has the steric hindrance of bigger compared to chain structures units such as alkyl, when crown ether knot For structure unit in macromolecule resin surface enrichment, the hindered phenol structure unit being connected with crown ether structures unit can be with macromolecule resin Long chain effectively tangle, this entanglement can supression crown ether structures fall off from resin surface, increase the antistatic of product Period.

The compound that the present invention synthesizes is compared with common hindered phenol compound, when hindered phenol structure content is suitable, Macromolecule resin is added as antioxidant, the compound synthesized in the present invention is because the hydrophilic lipophobic interaction of crown ether structures unit is in high score Sub- resin surface forms the enrichment of hindered phenol, and local high concentration hindered phenol is formed at the interface that macromolecule resin is contacted with air Unit so that its antioxidant effect is substantially better than common hindered phenol compound, while the compound that synthesizes of the present invention with it is general Logical hindered phenol compound is compared and is also equipped with apparent antistatic property.

The compound that the present invention synthesizes is compared with common crown ether compound, when crown ether structures content is suitable, as Antistatic agent is added macromolecule resin, because of the steric hindrance hindered phenol structure list containing bigger in the compound that synthesizes in the present invention Member, in the hydrophilic lipophobic interaction of crown ether structures unit when macromolecule resin surface forms the enrichment of hindered phenol, with crown ether structures list The connected hindered phenol structure unit of member can effectively tangle with the long chain of macromolecule resin, this entanglement can supression crown ether Structure falls off from resin surface, thus the antistatic period for the compound that the present invention synthesizes compared with common crown ether compound It is longer, while the compound that the present invention synthesizes also has antioxygenic property compared with common crown ether compound.

The compound that the present invention synthesizes forms mixed with common hindered phenol compound and common crown ether compound Object is closed to compare, when hindered phenol structure content and crown ether structures content homogeneously at that time, high score is added as antioxidant and antistatic agent Subtree fat, the compound that the present invention synthesizes is because of effect its antioxygen for mutually cooperateing with existing between crown ether unit and the phenol unit that is obstructed Change effect and anlistatig period are better than mixes what common hindered phenol compound and common crown ether compound formed Object is closed to be added among macromolecule resin.

Bulk of molecule is adjusted using the chain length of selected diol compound and dibromoalkane, such object can be changed in this way Compatibility of the matter in naval stores, to play best antioxidant effect.The method that the present invention uses also has anti-in each step Product yield in answering is higher, the easier feature of purification.

Nuclear-magnetism explanation

Wherein n is the positive integer of 3-16；M is the positive integer of 6-12.

¹H NMR (500Hz, DMSO), δ：9.05(S,2H),δ：7.07(S,4H),δ：4.45 (S, 4H), δ：3.62 (t, 4H), δ：(3.47-3.39 m, 36H), δ：(2.74-2.66 m, 12H), δ：2.45-1.82 (m, (4n+4m-16) H) δ：1.26 (S, 36H)。

Specific implementation mode

δ=9.05 indicates hindered phenol structure, δ in the nuclear-magnetism spectrum of compound：3.47-3.39 is indicated on crown ether close to oxygen atom CH₂Structure, δ：2.74-2.66 close to the CH of nitrogen-atoms on crown ether₂Representation.

The present invention is further described with reference to embodiment.The scope of the present invention is not restricted by the embodiments.

The raw material sources and its specification used in embodiment are as follows：

2,6- di-tert-butyl methyl phenols：Amresco analyses are pure；

Dimethyl suflfate：Amresco analyses are pure；

N- bromo-succinimides：The analysis of Chinese medicines group chemical reagent company is pure；

Azodiisobutyronitrile：The analysis of Chinese medicines group chemical reagent company is pure；

HO(CH₂)_nOH：FLUK analyses are pure；

To bromomethyl dimethyl isophthalate：FLUK analyses are pure；

Toluene 4- sulfonamide：FLUK analyses are pure

Triethylene-glycol：Lark prestige analyzes alcohol；

Ethylene oxide：The analysis of Tian Tai chemical reagents corporations is pure；

The diethyl ether solution of Boron tribromide：Lark prestige company analysis is pure；

Ethylene oxide：The analysis of Tian Tai chemical reagents corporations is pure；

Butyl titanate：The analysis of Tian Tai chemical reagents corporations is pure；

Lithium aluminium hydride：The analysis of lark prestige is pure；

Paratoluensulfonyl chloride：The analysis of Tian Tai chemical reagents corporations is pure.

Anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, dichloromethane, chloroform, carbon tetrachloride, first Alcohol, ethyl alcohol, acetone, dimethylformamide, triethylamine, toluene, benzene, dimethylbenzene, chlorobenzene, ethyl acetate, acetonitrile, n-hexane etc. with Upper solvent is that the analysis of Tianjin Tian Tai chemical companies is pure；

Polypropylene powder used in Comparison study example derives from Lanzhou Petrochemical Company, is chemical products；Antioxidant 1010, It is produced for Ciba, it is pure for chemistry；Antistatic agent hexadecyltrimethylammonium chloride Ciba product is pure for chemistry.

Embodiment 1

220g 2,6- di-tert-butyl methyl phenols and 150g dimethyl suflfates are dissolved in 2.5L dryings under nitrogen protection Among chloroform.Reaction solution is heated to 60 DEG C under being stirred among the three-necked flask of 5L, reaction continues 1.5 hours.Liquid cooling will be reacted But to being extracted repeatedly four times with the solution of potassium carbonate of 1L O.5mol/L after 25 DEG C, organic layer is dried 24 hours with anhydrous magnesium sulfate. Solvent is evaporated off the anhydrous magnesium sulfate drier being filtered to remove in solution under reduced pressure, obtains 2,6- di-t-butyls to methylbenzene Methyl ether 215.3g, yield 92%.

215.3g2,6- di-t-butyl p-methyl anisoles are added to the 5L equipped with 3L carbon tetrachloride under nitrogen protection Among three-necked flask.Then 161g N- bromo-succinimides and 2g azodiisobutyronitriles is added, reaction solution is heated to 77 DEG C Reaction stops heating after continuing 3 hours, after reaction solution is cooled to 0 DEG C, is filtered to remove white depositions, gained filtrate is being depressurized Lower removing solvent, crude product are recrystallized using n-hexane, obtain 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole 175.7g, yield is 61%.

By 175.7g 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole and 65g 1,3- propylene glycol be added to 5L three-necked flasks it In, then 2L acetone solvents and 39g Anhydrous potassium carbonates are added into flask.After reaction solution is heated to reflux 6 hours, heating dress is removed It sets, reaction solution is cooled to 25 DEG C.Decompression is lower remove obtained solid be dissolved into 1.5L ether after solvent among, with 1L distilled water Extract repeatedly three times, organic layer dilute solution of sodium bicarbonate and hydrochloric acid weak solution be extracted twice again after by the anhydrous sulphur of organic layer Sour magnesium is dried 12 hours.It is filtered to remove distillation under pressure after drier and removes solvent and obtain solid crude product, (solvent is column chromatography Chloroform, methanol) obtain mono- (3,5- di-t-butyls, 4- methoxyl groups) the methyl phenyl ethers anisole 117.6g of pure 1,3-PD, yield 68%.

By 117.6g1, mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of 3-propanediol, 281.5g1,6- dibromo-hexanes It is added in the three-necked flask containing 1.8L absolute ethyl alcohols 5L, is heated to reflux 10 hours with 15.4g sodium hydroxides.Heat filtering removes Filtrate decompression is evaporated by insoluble impurities, obtains solid crude product, and column chromatography (solvent dichloromethane, methanol) obtains pure [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 6- bromohexanes base] 1,3- the third diether 97.3g, yield 54%.

Under nitrogen protection, by 97.3g [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 6- bromohexanes base] 1,3- the third two Ether is added among the 5L three-necked flasks containing 1L dichloromethane, will be dissolved in advance after reacting liquid temperature is down to -20 DEG C Among the 1.5L dichloromethane solutions of 156g Boron tribromides are slowly added into flask with dropping funel, time for adding is 2 hours.Drop It is stirred 5 hours after reaction solution is restored to room temperature after adding.Reaction solution is transferred in separatory funnel, be added pH value 7~8 it Between distilled water, extract repeatedly after organic layer is separated afterwards three times with anhydrous magnesium sulfate dry 24 hours, be filtered to remove drier Pure [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 6- bromohexanes base] 1,3- the third two will be evaporated to obtain under filter vacuum afterwards Ether 92.5g, yield 98%.

By metallic sodium 119g, it is cut into silk and puts into stirring and dissolving in 1.5 ethyl alcohol, be cooled to room temperature, 892.9g toluene 4- is added Sulfonamide is heated to reflux 3h postcoolings to room temperature, and filtering with ethanol rinse, is dried to obtain 888.4g white solid product toluene Sulfonamide sodium yields：88.5%.

312.8g triethylene-glycols are dissolved in 500ml tetrahydrofurans in 5L flasks, 1200ml is then added and contains The aqueous solution of 47.6g NaOH is cooled to 0~5 DEG C with ice-water bath, the tetrahydrofuran of paratoluensulfonyl chloride 723.2g is slowly added dropwise Solution 1200ml, is added dropwise, and keeps the temperature at 0~5 DEG C and continues to be stirred to react 2h, stops reaction, pour the mixture into It is stirred in 660ml ice water, a large amount of white solids is precipitated, filtered, washed, it is dry, obtain the contractings of 764.9g bis- three with ethyl alcohol recrystallization Ethylene glycol diacid chloride white product, yield 80%.

888.4g toluenesulfonamide sodium is added in the DMF of 600mL and is heated with stirring to 80 DEG C, is cooled to room temperature, Xiang Ti 764.9g triethylene-glycol diacid chloride agitating and heatings are added in system and 80 DEG C of reaction 10h, decompression is kept to steam DMF, be added Mixed solution (the volume ratio 1 of 600ml methanol-waters：1, about 80 DEG C) stirring 30min, 80 DEG C of distilled water stirrings of 600ml are added 30min adds the sodium hydroxide solution that a concentration of 2mol/L temperature of 600ml is 80 DEG C and stirs, obtains Off-white solid, filter, It is dry, recrystallize to obtain 207.5g white products N, N- bis--(4- methylphenyls) acyl group 1 with second cyanogen, -18 crown- 6 of 10- diazas, Yield 25%.

Under nitrogen protection, lithium aluminium hydride 237.5g is added to 600mL tetrahydrofuran solutions in 5L three-neck flasks In, it stirs evenly, is slowly added to 207.5gN, N- bis--(4- methylphenyls) acyl group 1, -18 crown- 6 of 10- diazas is heated to reflux 72h restores to room temperature, the aqueous solution 1000mL (volume ratios 3 of THF is added：1) it quenches, filtering is spin-dried for, precipitation n-hexane weight Crystallization, obtains 19.6g white products 1, -18 crown- 6 of 10- diazas, yield 18%.

Under nitrogen protection, by 19.6g 1, -18 crown- 6 of 10- diazas and 9.82g epoxy second in 250mL round-bottomed flasks The methanol of 85ml is added in alkane mixing, and stirring is added for 24 hours, stops being added, and pressurization, which steams, obtains solid crude product after solvent, use just oneself Alkane is recrystallized to give 6 23.6g of -18 crown- of white solid N, N- diethyl alcohol radical -1,10- diaza.

By the N of 92.5g [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 6- bromohexanes base] 1,3- the third diether and 23.6g, The mixing of -18 crown- 6 of N- diethyl alcohol radicals -1,10- diaza is dissolved among the acetone of 500ml, while the potassium carbonate of 26.1g is added, will Reaction solution is heated to reflux 24 hours, and heat filtering removes insoluble impurities, and vacuum distillation removes solvent and obtains solid crude product, rear profit It uses column chromatography to obtain the pure N of 43.8g, { [(3,5- di-t-butyls, 4- hydroxyls) tolyl, the 6- hexyls] 1,3- of N- bis- Propylene glycol ether-ethyl } -18 crown- 6 of -1,10- diazas, yield 59%.

Embodiment 2

220g 2,6- di-tert-butyl methyl phenols and 150g dimethyl suflfates are dissolved in 2.5L dryings under nitrogen protection Among chloroform.Reaction solution is heated to 60 DEG C under being stirred among the three-necked flask of 5L, reaction continues 1.5 hours.Liquid cooling will be reacted But to being extracted repeatedly four times with the solution of potassium carbonate of 1LO.5mol/L after 25 DEG C, organic layer is dried 24 hours with anhydrous magnesium sulfate. Solvent is evaporated off in pressurization, obtains 2,6- di-t-butyls to methylbenzene first by the anhydrous magnesium sulfate drier being filtered to remove in solution Ether 215.3g, yield 92%.

215.3g2,6- di-t-butyl p-methyl anisoles are added to the 5L equipped with 3L carbon tetrachloride under nitrogen protection Among three-necked flask.Then 161g N- bromo-succinimides and 2g azodiisobutyronitriles is added, reaction solution is heated to 77 DEG C Reaction stops heating after continuing 3 hours, after reaction solution is cooled to 0 DEG C, is filtered to remove white depositions, gained filtrate is being depressurized Lower removing solvent, crude product are recrystallized using n-hexane, obtain 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole 175.7g, yield is 61%.

By 175.7g 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole and 101g1,6- hexylene glycols be added to 5L three-necked flasks it In, then 2L acetone solvents and 39g Anhydrous potassium carbonates are added into flask.After reaction solution is heated to reflux 10 hours, heating is removed Reaction solution is cooled to 25 DEG C by device.Decompression is lower remove obtained solid be dissolved into 1.5L ether after solvent among, distilled with 1L Water extracts three times repeatedly, organic layer dilute solution of sodium bicarbonate and hydrochloric acid weak solution be extracted twice again after by organic layer with anhydrous Magnesium sulfate is dried 12 hours.Distillation under pressure removing solvent obtains solid crude product, column chromatography (solvent after being filtered to remove drier For chloroform, methanol) obtain mono- (3,5- di-t-butyls, 4- methoxyl groups) the methyl phenyl ethers anisole 127.8g of pure 1,6- hexylene glycols, yield 65%.

By 127.8g1, mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of 6- hexylene glycols, bis- bromooctane of 299.7g1,8- It is added in the three-necked flask containing 1.8L absolute ethyl alcohols 5L, is heated to reflux 12 hours with 14.7g sodium hydroxides.Heat filtering removes Filtrate decompression is evaporated by insoluble impurities, obtains solid crude product, and column chromatography (solvent dichloromethane, methanol) obtains pure [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 8- bromooctanes base] own diether 100.8g of 1,6-, yield 51%.

Under nitrogen protection, by 100.8g [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 8- bromooctanes base] 1,6- oneself two Ether is added among the 5L three-necked flasks containing 1L dichloromethane, will be dissolved in advance after reacting liquid temperature is down to -20 DEG C Among the 1.5L dichloromethane solutions of 140g Boron tribromides are slowly added into flask with dropping funel, time for adding is 2 hours.Drop It is stirred 5 hours after reaction solution is restored to room temperature after adding.Reaction solution is transferred in separatory funnel, be added pH value 7~8 it Between distilled water, extract repeatedly after organic layer is separated afterwards three times with anhydrous magnesium sulfate dry 24 hours, be filtered to remove drier To be evaporated to obtain under filter vacuum afterwards pure [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 8- bromooctanes base] 1,6- oneself two Ether 95.2g, yield 97%.

By metallic sodium 106.1g, it is cut into stirring and dissolving in silk input 1L ethyl alcohol, is cooled to room temperature, 795.8g toluene 4- is added Sulfonamide is heated to reflux 3h postcoolings to room temperature, and filtering with ethanol rinse, is dried to obtain 791.8g white solid product toluene Sulfonamide sodium yields：88.5%.

278.8g triethylene-glycols are dissolved in 300ml tetrahydrofurans in 2.5L flasks, 900ml is then added and contains The aqueous solution of 42.4g NaOH is cooled to 0~5 DEG C with ice-water bath, the tetrahydrofuran of paratoluensulfonyl chloride 644.6g is slowly added dropwise Solution 850ml, is added dropwise, and keeps the temperature at 0~5 DEG C and continues to be stirred to react 2h, stops reaction, pour the mixture into It is stirred in 600ml ice water, a large amount of white solids is precipitated, filtered, washed, it is dry, obtain the contractings of 681.7g bis- three with ethyl alcohol recrystallization Ethylene glycol diacid chloride white product, yield 80%.

791.8g toluenesulfonamide sodium is added in the DMF of 600mL and is heated with stirring to 80 DEG C, is cooled to room temperature, Xiang Ti 681.7g triethylene-glycol diacid chloride agitating and heatings are added in system and 80 DEG C of reaction 10h, decompression is kept to steam DMF, be added Mixed solution (the volume ratio 1 of 600ml methanol-waters：1, about 80 DEG C) stirring 30min, 80 DEG C of distilled water stirrings of 600ml are added 30min adds the sodium hydroxide solution that a concentration of 2mol/L temperature of 600ml is 80 DEG C and stirs, obtains Off-white solid, filter, It is dry, recrystallize to obtain 184.9g white products N, N- bis--(4- methylphenyls) acyl group 1 with second cyanogen, -18 crown- 6 of 10- diazas, Yield 25%.

Under nitrogen protection, lithium aluminium hydride 211.7g is added to 550mL tetrahydrofuran solutions in 2.5L three-neck flasks In, it stirs evenly, is slowly added to 184.9gN, N- bis--(4- methylphenyls) acyl group 1, -18 crown- 6 of 10- diazas is heated to reflux 72h restores to room temperature, the aqueous solution 800mL (volume ratios 3 of THF is added：1) it quenches, filtering is spin-dried for, precipitation is tied again with n-hexane Crystalline substance obtains 17.5g white products 1, -18 crown- 6 of 10- diazas, yield 18%.

Under nitrogen protection, by 17.5g 1, -18 crown- 6 of 10- diazas and 9.8g epoxy second in 250mL round-bottomed flasks The methanol of 100ml is added in alkane mixing, and stirring is added for 24 hours, stops being added, pressurization obtains solid crude product after steaming solvent, with just Hexane is recrystallized to give -18 crown- 6 of 21.08g white solids N, N- diethyl alcohol radical -1,10- diaza.

By the N, N- of 95.2g [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 8- octyls] 1,6- own diether and 21.08g The mixing of -18 crown- 6 of diethyl alcohol radical -1,10- diaza is dissolved among the acetone of 500ml, while the potassium carbonate of 23.3g is added, will be anti- Liquid is answered to be heated to reflux 24 hours, heat filtering removes insoluble impurities, and vacuum distillation removes solvent and obtains solid crude product, rear to utilize Column chromatography for separation obtains the pure N of 43.4g, N- bis- [(3,5- di-t-butyls, 4- hydroxyls) tolyl, 8- octyls] 1,6- oneself Glycol ether-ethyl } -18 crown- 6 of -1,10- diazas, yield 58%.

Embodiment 3

220g 2,6- di-tert-butyl methyl phenols and 150g dimethyl suflfates are dissolved in 2.5L dryings under nitrogen protection Among chloroform.Reaction solution is heated to 60 DEG C under being stirred among the three-necked flask of 5L, reaction continues 1.5 hours.Liquid cooling will be reacted But to being extracted repeatedly four times with the solution of potassium carbonate of 1LO.5mol/L after 25 DEG C, organic layer is dried 24 hours with anhydrous magnesium sulfate. Solvent is evaporated off the anhydrous magnesium sulfate drier being filtered to remove in solution under reduced pressure, obtains 2,6- di-t-butyls to methylbenzene Methyl ether 215.3g, yield 92%.

215.3g2,6- di-t-butyl p-methyl anisoles are added to the 5L equipped with 3L carbon tetrachloride under nitrogen protection Among three-necked flask.Then 161g N- bromo-succinimides and 2g azodiisobutyronitriles is added, reaction solution is heated to 77 DEG C Reaction stops heating after continuing 3 hours, after reaction solution is cooled to 0 DEG C, is filtered to remove white depositions, gained filtrate is being depressurized Lower removing solvent, crude product are recrystallized using n-hexane, obtain 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole 175.7g, yield is 61%.

175.7g 2,6- di-t-butyls are added to 5L three-necked flasks to bromomethyl methyl phenyl ethers anisole and 147g1,10- decanediols Among, then 2L anhydrous ethanol solvents and 22.6g sodium hydroxides are added into flask.After reaction solution is heated to reflux 15 hours, remove Heating device is removed, reaction solution is cooled to 25 DEG C.Decompression is lower remove obtained solid be dissolved into 1.5L ether after solvent among, use 1L distilled water extracts three times repeatedly, organic layer dilute solution of sodium bicarbonate and hydrochloric acid weak solution be extracted twice again after by organic layer It is dried 24 hours with anhydrous magnesium sulfate.Distillation under pressure removing solvent obtains solid crude product, column chromatography after being filtered to remove drier (solvent is chloroform, methanol) obtains mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of pure 1,10- decanediols 141.5g yield 62%.

By 141.5g1, mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of 10- decanediols, 315g1,10- dibromo-decanes It is added in the three-necked flask containing 1.8L absolute ethyl alcohols 5L, is heated to reflux 16 hours with 14.0g sodium hydroxides.Heat filtering removes Filtrate decompression is evaporated by insoluble impurities, obtains solid crude product, and column chromatography (solvent dichloromethane, methanol) obtains pure [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 10- bromo-decanes base] 1,10- last of the ten Heavenly stems diether 102.5g, yield 47%.

Under nitrogen protection, by 102.5g [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 10- bromo-decanes base] 1, the 10- last of the ten Heavenly stems Diether is added among the 5L three-necked flasks containing 1L dichloromethane, will be dissolved in advance after reacting liquid temperature is down to -20 DEG C Among the 1.5L dichloromethane solutions of 124.2g Boron tribromides are slowly added into flask with dropping funel, time for adding is 2 hours. It is stirred 5 hours after reaction solution is restored to room temperature after dripping.Reaction solution is transferred in separatory funnel, pH value is added 7~8 Between distilled water, extract repeatedly after organic layer is separated afterwards three times with anhydrous magnesium sulfate dry 24 hours, be filtered to remove drying It will be evaporated to obtain pure [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 10- bromo-decanes base] 1,10- under filter vacuum after agent Last of the ten Heavenly stems diether 96.2g, yield 96%.

By metallic sodium 92.6g, it is cut into stirring and dissolving in silk input 1L ethyl alcohol, is cooled to room temperature, 694.4g toluene 4- is added Sulfonamide is heated to reflux 3h postcoolings to room temperature, and filtering with ethanol rinse, is dried to obtain 691.0g white solid product toluene Sulfonamide sodium yields：88.5%.

243.3g triethylene-glycols are dissolved in 220ml tetrahydrofurans in 2.5L flasks, 900ml is then added and contains The aqueous solution of 37g NaOH is cooled to 0~5 DEG C with ice-water bath, and the tetrahydrofuran that paratoluensulfonyl chloride 562.5g is slowly added dropwise is molten Liquid 850ml, is added dropwise, and keeps the temperature at 0~5 DEG C and continues to be stirred to react 2h, stops reaction, pour the mixture into 450ml It is stirred in ice water, a large amount of white solids is precipitated, filtered, washed, it is dry, obtain 594.9g triethylene-glycols with ethyl alcohol recrystallization Diacid chloride white product, yield 80%.

691.0g toluenesulfonamide sodium is added in the DMF of 450mL and is heated with stirring to 80 DEG C, is cooled to room temperature, Xiang Ti 594.7g triethylene-glycol diacid chloride agitating and heatings are added in system and 80 DEG C of reaction 10h, decompression is kept to steam DMF, be added Mixed solution (the volume ratio 1 of 500ml methanol-waters：1, about 80 DEG C) stirring 30min, 80 DEG C of distilled water stirrings of 500ml are added 30min adds the sodium hydroxide solution that a concentration of 2mol/L temperature of 500ml is 80 DEG C and stirs, obtains Off-white solid, filter, It is dry, recrystallize to obtain 161.4g white products N, N- bis--(4- methylphenyls) acyl group 1 with second cyanogen, -18 crown- 6 of 10- diazas, Yield 25%.

Under nitrogen protection, lithium aluminium hydride 184.7g is added to 450mL tetrahydrofuran solutions in 2.5L three-neck flasks In, it stirs evenly, is slowly added to 161.4gN, N- bis--(4- methylphenyls) acyl group 1, -18 crown- 6 of 10- diazas is heated to reflux 72h restores to room temperature, the aqueous solution 900mL (volume ratios 3 of THF is added：1) it quenches, filtering is spin-dried for, precipitation is tied again with n-hexane Crystalline substance obtains 15.3g white products 1, -18 crown- 6 of 10- diazas, yield 18%.

Under nitrogen protection, by 15.3g 1, -18 crown- 6 of 10- diazas and 7.64g epoxy second in 250mL round-bottomed flasks The methanol of 45ml is added in alkane mixing, and stirring is added for 24 hours, stops being added, and pressurization, which steams, obtains solid crude product after solvent, use just oneself Alkane is recrystallized to give 6 18.37g of -18 crown- of white solid N, N- diethyl alcohol radical -1,10- diaza.

By 96.2g [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 10- bromo-decanes base] 1,10- last of the ten Heavenly stems diether and 18.37g The mixing of -18 crown- 6 of N, N- diethyl alcohol radical -1,10- diaza is dissolved among the acetone of 500ml, while the potassium carbonate of 20.3g is added, Reaction solution is heated to reflux 24 hours, heat filtering removes insoluble impurities, and vacuum distillation removes solvent and obtains solid crude product, after The pure N of 40.7g are obtained using column chromatography for separation, N- bis- [(3,5- di-t-butyls, 4- hydroxyls) tolyl, 10- decyls] 1, 10- decanediols ether-ethyl } -18 crown- 6 of -1,10- diazas, yield 55%.

Embodiment 4

220g 2,6- di-tert-butyl methyl phenols and 150g dimethyl suflfates are dissolved in 2.5L dryings under nitrogen protection Among chloroform.Reaction solution is heated to 60 DEG C under being stirred among the three-necked flask of 5L, reaction continues 1.5 hours.Liquid cooling will be reacted But to being extracted repeatedly four times with the solution of potassium carbonate of 1LO.5mol/L after 25 DEG C, organic layer is dried 24 hours with anhydrous magnesium sulfate. Solvent is evaporated off the anhydrous magnesium sulfate drier being filtered to remove in solution under reduced pressure, obtains 2,6- di-t-butyls to methylbenzene Methyl ether 215.3g, yield 92%.

215.3g2,6- di-t-butyl p-methyl anisoles are added to the 5L equipped with 3L carbon tetrachloride under nitrogen protection Among three-necked flask.Then 161g N- bromo-succinimides and 2g azodiisobutyronitriles is added, reaction solution is heated to 77 DEG C Reaction stops heating after continuing 3 hours, after reaction solution is cooled to 0 DEG C, is filtered to remove white depositions, gained filtrate is being depressurized Lower removing solvent, crude product are recrystallized using n-hexane, obtain 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole 175.7g, yield is 61%.

175.7g 2,6- di-t-butyls are added to tri- mouthfuls of 5L to bromomethyl methyl phenyl ethers anisole and 12 glycol of 171.2g1,12- Among flask, then 2L anhydrous ethanol solvents and 22.6g sodium hydroxides are added into flask.Reaction solution is heated to reflux 18 hours Afterwards, heating device is removed, reaction solution is cooled to 25 DEG C.Decompression is lower remove after solvent by obtained solid be dissolved into 1.5L ether it In, it is extracted repeatedly three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and hydrochloric acid weak solution will after being extracted twice again Organic layer is dried 24 hours with anhydrous magnesium sulfate.Distillation under pressure removing solvent obtains solid crude product after being filtered to remove drier, Column chromatography (solvent is chloroform, methanol) obtains mono- (3,5- di-t-butyls, the 4- methoxyl groups) benzene of pure 1,12-, 12 glycol Methyl ether 146.4g, yield 60%.

By 146.4g1, mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of 12 glycol of 12-, 305.1g1,10- dibromos Decane and 13.6g sodium hydroxides are added in the three-necked flask containing 1.8L absolute ethyl alcohols 5L, are heated to reflux 20 hours.Heat filtering Insoluble impurities is removed, filtrate decompression is evaporated, solid crude product is obtained, column chromatography (solvent dichloromethane, methanol) obtains Pure 12 diether 97.0g of [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 10- bromo-decanes base] 1,12-, yield 44%.

Under nitrogen protection, by 97.0g [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 10- bromo-decanes base] 1,12- ten Two diether are added among the 5L three-necked flasks containing 1L dichloromethane, will be dissolved in advance after reacting liquid temperature is down to -20 DEG C Among having the 1.5L dichloromethane solutions of 112.2g Boron tribromides to be slowly added into flask with dropping funel, time for adding is 2 small When.It is stirred 5 hours after reaction solution is restored to room temperature after dripping.Reaction solution is transferred in separatory funnel, pH value is added 7 Distilled water between~8 is extracted and is dried 24 hours with anhydrous magnesium sulfate after three times afterwards separating organic layer, is filtered to remove dry repeatedly It will be evaporated to obtain pure [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 10- bromo-decanes base] 1 under filter vacuum after drying prescription, 12 diether 89.2g of 12-, yield 94%.

By metallic sodium 82.1g, it is cut into stirring and dissolving in silk input 1L ethyl alcohol, is cooled to room temperature, 616g toluene 4- sulphurs is added Amide is heated to reflux 3h postcoolings to room temperature, and filtering with ethanol rinse, is dried to obtain 612.9g white solid product toluene sulphurs Amide sodium yields：88.5%.

215.8g triethylene-glycols are dissolved in 220ml tetrahydrofurans in 2.5L flasks, 800ml is then added and contains The aqueous solution of 32.9g NaOH is cooled to 0~5 DEG C with ice-water bath, and the tetrahydrofuran that paratoluensulfonyl chloride 499g is slowly added dropwise is molten Liquid 800ml, is added dropwise, and keeps the temperature at 0~5 DEG C and continues to be stirred to react 2h, stops reaction, pour the mixture into 430ml It is stirred in ice water, a large amount of white solids is precipitated, filtered, washed, it is dry, obtain 527.7g triethylene-glycols with ethyl alcohol recrystallization Diacid chloride white product, yield 80%.

612.9g toluenesulfonamide sodium is added in the DMF of 420mL and is heated with stirring to 80 DEG C, is cooled to room temperature, Xiang Ti 527.7g triethylene-glycol diacid chloride agitating and heatings are added in system and 80 DEG C of reaction 10h, decompression is kept to steam DMF, be added Mixed solution (the volume ratio 1 of 500ml methanol-waters：1, about 80 DEG C) stirring 30min, 500ml80 DEG C of distilled water stirring is added 30min adds the sodium hydroxide solution that a concentration of 2mol/L temperature of 500ml is 80 DEG C and stirs, obtains Off-white solid, filter, It is dry, recrystallize to obtain 143.2g white products N, N- bis--(4- methylphenyls) acyl group 1 with second cyanogen, -18 crown- 6 of 10- diazas, Yield 25%.

Under nitrogen protection, lithium aluminium hydride 163.9g is added to 400mL tetrahydrofuran solutions in 2.5L three-neck flasks In, it stirs evenly, is slowly added to 143.2gN, N- bis--(4- methylphenyls) acyl group 1, -18 crown- 6 of 10- diazas is heated to reflux 72h restores to room temperature, the aqueous solution 800mL (volume ratios 3 of THF is added：1) it quenches, filtering is spin-dried for, precipitation is tied again with n-hexane Crystalline substance obtains 13.6g white products 1, -18 crown- 6 of 10- diazas, yield 18%.

Under nitrogen protection, by 13.6g 1, -18 crown- 6 of 10- diazas and 6.78g epoxy second in 250mL round-bottomed flasks The methanol of 50ml is added in alkane mixing, and stirring is added for 24 hours, stops being added, and pressurization, which steams, obtains solid crude product after solvent, use just oneself Alkane is recrystallized to give -18 crown- 6 of 16.29g white solids N, N- diethyl alcohol radical -1,10- diaza.

By 12 diether of 89.2g [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 10- bromo-decanes base] 1,12- and 16.29g N, the mixing of -18 crown- 6 of N- diethyl alcohol radicals -1,10- diaza is dissolved among the acetone of 500ml, while the potassium carbonate of 18g is added, Reaction solution is heated to reflux 24 hours, heat filtering removes insoluble impurities, and vacuum distillation removes solvent and obtains solid crude product, after The pure N of 35.5g are obtained using column chromatography for separation, N- bis- [(3,5- di-t-butyls, 4- hydroxyls) tolyl, 10- decyls] 1, 12 glycol ethers of 12--ethyl } -18 crown- 6 of -1,10- diazas, yield 52%.

Embodiment 5

220g 2,6- di-tert-butyl methyl phenols and 150g dimethyl suflfates are dissolved in 2.5L dryings under nitrogen protection Among chloroform.Reaction solution is heated to 60 DEG C under being stirred among the three-necked flask of 5L, reaction continues 1.5 hours.Liquid cooling will be reacted But to being extracted repeatedly four times with the solution of potassium carbonate of 1LO.5mol/L after 25 DEG C, organic layer is dried 24 hours with anhydrous magnesium sulfate. Solvent is evaporated off the anhydrous magnesium sulfate drier being filtered to remove in solution under reduced pressure, obtains 2,6- di-t-butyls to methylbenzene Methyl ether 215.3g, yield 92%.

215.3g2,6- di-t-butyl p-methyl anisoles are added to the 5L equipped with 3L carbon tetrachloride under nitrogen protection Among three-necked flask.Then 161g N- bromo-succinimides and 2g azodiisobutyronitriles is added, reaction solution is heated to 77 DEG C Reaction stops heating after continuing 3 hours, after reaction solution is cooled to 0 DEG C, is filtered to remove white depositions, gained filtrate is being depressurized Lower removing solvent, crude product are recrystallized using n-hexane, obtain 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole 175.7g, yield is 61%.

175.7g 2,6- di-t-butyls are added to tri- mouthfuls of 5L to bromomethyl methyl phenyl ethers anisole and 16 glycol of 191.5g1,16- Among flask, then 2L anhydrous ethanol solvents and 31.6g potassium hydroxide are added into flask.Reaction solution is heated to reflux 24 hours Afterwards, heating device is removed, reaction solution is cooled to 25 DEG C.Decompression is lower remove after solvent by obtained solid be dissolved into 1.5L ether it In, it is extracted repeatedly three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and hydrochloric acid weak solution will after being extracted twice again Organic layer is dried 24 hours with anhydrous magnesium sulfate.Distillation under pressure removing solvent obtains solid crude product after being filtered to remove drier, Column chromatography (solvent is chloroform, methanol) obtains mono- (3,5- di-t-butyls, the 4- methoxyl groups) benzene of pure 1,16-, 16 glycol Methyl ether 151.6g, yield 55%.

By 151.6g 1, mono- (3,5- di-t-butyls, the 4- methoxyl groups) methyl phenyl ethers anisole of 16 glycol of 16-, 305.1g1,12- bis- Bromo-dodecane and 12.4g sodium hydroxides are added in the three-necked flask containing 1.8L absolute ethyl alcohols 5L, are heated to reflux 24 hours.Heat It is filtered to remove insoluble impurities, filtrate decompression is evaporated, obtains solid crude product, column chromatography (solvent dichloromethane, methanol) Pure 16 diether 95.6g of [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 12- bromo-dodecanes base] 1,16- are obtained, are produced Rate 42%.

Under nitrogen protection, by 95.6g [(3,5- di-t-butyls, 4- methoxyl groups) benzyl, 12- bromo-dodecanes base] 1,16- 16 diether are added among the 5L three-necked flasks containing 1L dichloromethane, will be molten in advance after reacting liquid temperature is down to -20 DEG C Among solution has the 1.5L dichloromethane solutions of 97.9g Boron tribromides to be slowly added into flask with dropping funel, time for adding is 2 small When.It is stirred 5 hours after reaction solution is restored to room temperature after dripping.Reaction solution is transferred in separatory funnel, pH value is added 7 Distilled water between~8 is extracted and is dried 24 hours with anhydrous magnesium sulfate after three times afterwards separating organic layer, is filtered to remove dry repeatedly It will be evaporated to obtain pure [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 12- bromo-dodecanes base] 1 under filter vacuum after drying prescription, 16 diether 85.3g of 16-, yield 91%.

By metallic sodium 69.3g, it is cut into stirring and dissolving in silk input 800ml ethyl alcohol, is cooled to room temperature, 519.9g toluene is added 4- sulfonamide is heated to reflux 3h postcoolings to room temperature, and filtering with ethanol rinse, is dried to obtain 517.3g white solid product first Benzsulfamide sodium yields：88.5%.

182.1g triethylene-glycols are dissolved in 185ml tetrahydrofurans in 2.5L flasks, 700ml is then added and contains The aqueous solution of 27.7g NaOH is cooled to 0~5 DEG C with ice-water bath, the tetrahydrofuran of paratoluensulfonyl chloride 412.1g is slowly added dropwise Solution 700ml, is added dropwise, and keeps the temperature at 0~5 DEG C and continues to be stirred to react 2h, stops reaction, pour the mixture into It is stirred in 350ml ice water, a large amount of white solids is precipitated, filtered, washed, it is dry, obtain the contractings of 445.4g bis- three with ethyl alcohol recrystallization Ethylene glycol diacid chloride white product, yield 80%.

517.3g toluenesulfonamide sodium is added in the DMF of 300mL and is heated with stirring to 80 DEG C, is cooled to room temperature, Xiang Ti 445.4g triethylene-glycol diacid chloride agitating and heatings are added in system and 80 DEG C of reaction 10h, decompression is kept to steam DMF, be added Mixed solution (the volume ratio 1 of 400ml methanol-waters：1, about 80 DEG C) stirring 30min, 80 DEG C of distilled water stirrings of 400ml are added 30min adds the sodium hydroxide solution that a concentration of 2mol/L temperature of 400ml is 80 DEG C and stirs, obtains Off-white solid, filter, It is dry, recrystallize to obtain 120.8g white products N, N- bis--(4- methylphenyls) acyl group 1 with second cyanogen, -18 crown- 6 of 10- diazas, Yield 25%.

Under nitrogen protection, lithium aluminium hydride 138.3g is added to 300mL tetrahydrofuran solutions in 2.5L three-neck flasks In, it stirs evenly, is slowly added to 120.8gN, N- bis--(4- methylphenyls) acyl group 1, -18 crown- 6 of 10- diazas is heated to reflux 72h restores to room temperature, the aqueous solution 700mL (volume ratios 3 of THF is added：1) it quenches, filtering is spin-dried for, precipitation is tied again with n-hexane Crystalline substance obtains 11.4g white products 1, -18 crown- 6 of 10- diazas, yield 18%.

Under nitrogen protection, by 11.4g 1, -18 crown- 6 of 10- diazas and 5.7g epoxy second in 500mL round-bottomed flasks The methanol of 50ml is added in alkane mixing, and stirring is added for 24 hours, stops being added, and pressurization, which steams, obtains solid crude product after solvent, use just oneself Alkane is recrystallized to give -18 crown- 6 of 13.76g white solids N, N- diethyl alcohol radical -1,10- diaza.

By 16 diether of 85.3g [(3,5- di-t-butyls, 4- hydroxyls) benzyl, 12- bromo-dodecanes base] 1,16-, with The mixing of -18 crown- 6 of the N of 13.76g, N- diethyl alcohol radical -1,10- diaza is dissolved among the acetone of 500ml, while 15.2g is added Potassium carbonate, reaction solution is heated to reflux 24 hours, heat filtering remove insoluble impurities, vacuum distillation remove solvent obtain solid Crude product obtains the pure N of 32.8g, N- bis- { [(3,5- di-t-butyls, 4- hydroxyls) tolyl, 12- using column chromatography for separation afterwards Dodecyl] 1,16-, 16 glycol ethers-ethyl } -18 crown- 6 of -1,10- diazas, yield 51%.

Application examples：

Formulation samples：100 mass parts polypropylene powders are mixed with 1 mass parts Additives Products in high-speed mixer Even, with double screw extruder extruding pelletization, double-screw extruder screw rotating speed is 120 revs/min, and material melt temperature is 220 DEG C. Three [1,16- ten six mono- (3,5- di-t-butyls, the 4- hydroxyls) methyl phenyl ethers anisole of glycol] phosphite esters in comparative example according to 6 the method for embodiment is made in CN103319523A, two [1,16- ten six mono- (3,5- di-t-butyls, the 4- hydroxyls) benzene of glycol Methyl ether] base pentaerythritol diphosphite according to 6 the method for embodiment in CN103319537A be made, formulation samples are resisted Oxidisability and antistatic property are measured that the results are shown in table below：

Table 1, the inoxidizability of formulation samples and antistatic property are tested

It can be seen that when polypropylene does not add antioxidant and antistatic agent in comparative example 1, produce by the result of table 1 Product are very easy to be aoxidized, and show that melting means is big, and yellow colour index is high, and the initial dusting time is short；Its resin surface resistance is high simultaneously, Internal charge can not be overflowed by surface, easy to produce electrostatic.When comparative example 2 is added to four [β-of antioxidant in polypropylene (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester when, product is not easy to be aoxidized, but sheet resistance is high, internal Charge can not be overflowed by surface, easy to produce electrostatic.Antistatic agent N, N- bis--(16 is added in 3 polypropylene of comparative example Alkyl) -1,10- diazas -18 after crown- 6 its show certain antistatic property, but product is very easy to be aoxidized, and shows Melting means is big, and yellow colour index is high, and the initial dusting time is short.[β-(3,5- di-t-butyls-the 4- of antioxidant four are added simultaneously in comparative example 4 Hydroxy phenyl) propionic acid] pentaerythritol ester and antistatic agent N, N- bis---18 crown- 6 of (cetyl) -1,10- diazas, two kinds are helped Agent maintains its anti-oxidant or antistatic effect having, but shows without collaboration enhancing effect between two kinds of auxiliary agents.5 He of comparative example The hindered phenol phosphite ester that comparative example 6 is added to CN 103319523A and CN103319537A synthesis respectively in polypropylene is double Function antioxidant, antioxidant effect is more preferable, and it is longer to show as the initial dusting time, but it does not have antistatic effect, performance For but sheet resistance it is high, internal charge can not be overflowed by surface, easy to produce electrostatic.When in acrylic resin in application examples After being added to the hindered phenol synthesized in embodiment and crown ether bifunctional compound, inoxidizability was not only shown but also had shown anti-quiet Electrically, and the synergistic effect between hindered phenol and crown ether difunctional makes two kinds of effects be reinforced.

Claims (19)

1. a kind of dual-function compound including hindered phenol and crown ether structures, it is characterised in that structural formula is：

The positive integer that wherein n is 3~16；The positive integer that m is 6~12.

2. a kind of synthetic method of compound as described in claim 1, it is characterised in that include the following steps：

1st step, the protection of phenolic hydroxyl group：It is 1 in molar ratio by 2,6- di-tert-butyl methyl phenols and dimethyl suflfate：1.1~2 It is added in reaction dissolvent, under nitrogen protection, reaction temperature is 45 DEG C~61 DEG C, and the reaction time is 0.1h~2h, generates 2,6- Di-t-butyl p-methyl anisole；

2nd step, the α bromos of 2,6- di-t-butyl p-methyl anisoles：By 2,6- di-t-butyls p-methyl anisole and N- bromos Succimide is 1 in molar ratio：1~1.5 is added reactor, while reaction dissolvent is added, under nitrogen protection and in azo Under the catalytic action of bis-isobutyronitrile, 50 DEG C~77 DEG C of reaction temperature, 2~5 hours reaction time generates 2,6- di-t-butyls to bromine Methylanisole；

3rd step, alcoholization reaction of 2, the 6- di-t-butyls to bromomethyl methyl phenyl ethers anisole：By 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole and Glycol compound is 1 in molar ratio：1.1~3 are added reactor, while being added with 2,6- di-t-butyls to bromomethyl methyl phenyl ethers anisole The alkaline matter of equimolar amounts, is then added reaction dissolvent, and reaction solution is heated to flowing back, 5~60 hours reaction time, generates 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole；

4th step, the bromination reaction of 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole：Made from the reaction of upper step 1, n-n glycol list (3,5- di-t-butyls are to methoxyl group) methyl phenyl ethers anisole is 1 according to molar ratio with straight chain dibromoalkane：3~5 are added instead Device is answered, while the alkaline matter with 3,5- di-t-butyls to methyl oxygroup methyl phenyl ethers anisole alcohol equimolar amounts is added, reaction is then added Reaction solution is heated to reflux 10~48 hours by solvent, is filtered to remove insoluble impurities, and vacuum distillation removes solvent and obtains solids crude Product obtains pure bromo-derivative [(3,5- di-t-butyls, 4- methoxyl groups) tolyl, m- bromine m alkane using column chromatography for separation afterwards Base] 1, n-n diether；

The deprotection reaction of 5th step hydroxyl：It is 3 in molar ratio by the bromo-derivative of the 4th step reaction gained and Boron tribromide：1~3 adds Enter reactor；Reaction dissolvent is added simultaneously to be reacted, reaction products therefrom is added in the reaction vessel containing dichloromethane, After reacting liquid temperature is down to 0~-50 DEG C, the dichloromethane solution in advance dissolved with Boron tribromide is added drop-wise to reaction vessel In, it is stirred 2~5 hours after reaction solution is restored to room temperature after dripping, obtain [(3,5- di-t-butyls, 4- hydroxyls) tolyl, M- bromine m alkyl] 1, n-n diether；

6th step, the preparation of Chloramine：Metallic sodium is cut into stirring and dissolving in silk input solvent, controlled concentration is 0.01~0.03g/ml is cooled to room temperature, and the toluene 4- sulfonamide for being 0.5~2 with metallic sodium molar ratio is added, is heated to reflux 1 ~6h postcoolings to room temperature, filtering with eluent solvent, is dried to obtain solid product toluenesulfonamide sodium；

7th step, the sulfonylation of triethylene-glycol：Triethylene-glycol is dissolved in solvent in the reaction vessel, then The sodium hydrate aqueous solution for being 2~4 with triethylene-glycol molar ratio is added, is cooled to 0~5 DEG C with ice-water bath, is slowly added dropwise The solution for the paratoluensulfonyl chloride for being 1.5~3 with triethylene-glycol molar ratio, is added dropwise, keeps the temperature at 0~5 DEG C Continue to be stirred to react 1~5h, stop reaction, pour the mixture into ice water and stir, white solid is precipitated, filter, wash, does It is dry, obtain white double p-methylbenzoic acid Triethylene Glycol products with solvent recrystallization；

8th step, the annulation of triethylene-glycol：Toluenesulfonamide sodium made from 6th step is added to stirring in solvent to add Heat is cooled to room temperature to 60~100 DEG C, and it is 3~1 to be added into system with the 6th step product molar ratio:White production is made in 1 the 7th step Object agitating and heating simultaneously keeps 60~100 DEG C of 5~20h of reaction, decompression to steam solvent, and the mixed solution that methanol and water is added stirs 0.5~1h is added 60~100 DEG C of distilled water and stirs 0.5~1h, adds 60~100 DEG C of the hydrogen-oxygen of a concentration of 1~5mol/L Change sodium solution stirring, obtain Off-white solid, filter, it is dry, obtain white N with solvent recrystallization, N- bis- to methyl benzoyl -1, 6 product of -18 crown- of 10- diazas；

9th step, the preparation of -18 crown- 6 of 1,10- diaza：Under nitrogen protection, lithium aluminium hydride is added in the reaction vessel In solvent, controlled concentration is 35~80g/L, is stirred evenly, and the white product of the 8th step is added, and controls the white product and hydrogenation The molar ratio of lithium aluminium is 0.02~0.1, is heated to reflux 60~90h, is restored to room temperature, be added volumetric concentration be 50~80% it is molten The aqueous solution of agent, filtering, steams solvent, recrystallizes, obtains white product；

10th step, the preparation of crown ether glycol：Under nitrogen gas shielded, in the reaction vessel by -18 crown- 6 of 1,10- diazas and ring Oxidative ethane in molar ratio 1：1~3 mixing is added solvent and is heated to reflux 2~for 24 hours, is cooled to room temperature, and decompression steams solvent, weight Crystallization obtains N, 6 white crystal of -18 crown- of N- diethyl alcohol radical -1,10- diazas；

11st step, the preparation of hindered phenol-crown ether Amphi-pathic compound：5th step is reacted into bromo-derivative obtained and N made from upper step, - 18 crown- 6 of N- diethyl alcohol radical -1,10- diazas in molar ratio 3~1:3 mixing, while being added and the equimolar alkalinity of bromo-derivative Substance is added reaction dissolvent, reaction solution is heated to reflux 10~48 hours, and heat filtering removes insoluble impurities, and vacuum distillation removes It goes solvent to obtain solid crude product, obtains clean product N, N- bis- { [(3,5- di-t-butyls, 4- hydroxyls using column chromatography for separation afterwards Base) tolyl, m-m alkyl] 1, n-n glycol ether-ethyl } -18 crown- 6 of -1,10- diazas.

3. synthetic method as claimed in claim 2, it is characterised in that be used for bromo described in the 3rd step, the 4th step and the 11st step The alkaline matter that object is reacted with alcohol is sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate.

4. synthetic method as claimed in claim 2, it is characterised in that the carbon atom number of the glycol compound described in the 3rd step For 3~16 positive integer.

5. synthetic method as claimed in claim 2, it is characterised in that the carbon atom number of the straight chain dibromoalkane described in the 4th step For 6~12 positive integer.

6. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 1st step is selected from chlorobenzene, two One kind in chloromethanes, chloroform, toluene.

7. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 2nd step is selected from benzene, dichloro One kind in methane, chloroform, carbon tetrachloride.

8. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 3rd step is selected from methanol, second One kind in alcohol, acetone, dimethylformamide.

9. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 4th step be selected from triethylamine, One kind in ethyl alcohol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate.

10. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 5th step is selected from dichloromethane One kind in alkane, chloroform, carbon tetrachloride.

11. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 6th step is selected from ethyl alcohol, first One kind in alcohol, chloroform, dichloromethane.

12. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 7th step is selected from tetrahydrochysene furan It mutters, one kind in dichloromethane, chloroform, carbon tetrachloride.

13. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 8th step is selected from dimethyl One kind in sulfoxide, dimethylformamide, tetrahydrofuran, acetonitrile.

14. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 9th step is selected from tetrahydrochysene furan It mutters, one kind in dichloromethane, chloroform, carbon tetrachloride.

15. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 10th step be selected from ethyl alcohol, One kind in methanol, chloroform, dichloromethane.

16. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent being added in the 11st step is selected from three second One kind in amine, ethyl alcohol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate.

17. synthetic method as claimed in claim 2, it is characterised in that the Boron tribromide being added in the 5th step is mass concentration For the diethyl ether solution of 17% Boron tribromide.

18. synthetic method as claimed in claim 2, it is characterised in that reaction solution is cooled to room temperature after the reaction was complete by the 1st step, Dilute potassium carbonate solution is added into reaction solution to be extracted, is evaporated after organic phase drying and can be obtained pure 2,6- di-t-butyls P-methyl anisole.

19. a kind of application of compound as described in claim 1, it is characterised in that the compound is as the anti-of vistanex Oxidant and antistatic agent use, and are added in vistanex base-material for 0.01%~1% according to mass percent.