CN100484911C - Methoxy phenyl paradioxybenzene, synthetic method and application in synthesizing polymeric material - Google Patents
Methoxy phenyl paradioxybenzene, synthetic method and application in synthesizing polymeric material Download PDFInfo
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- CN100484911C CN100484911C CNB2005100167462A CN200510016746A CN100484911C CN 100484911 C CN100484911 C CN 100484911C CN B2005100167462 A CNB2005100167462 A CN B2005100167462A CN 200510016746 A CN200510016746 A CN 200510016746A CN 100484911 C CN100484911 C CN 100484911C
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Abstract
A methoxyphenyl hydroquinone (2-(3-methoxyphenyl)hydroquinone and 2-(2,5-dimethoxyphenyl)hydroquinone) is prepared through reaction between methoxyphenylamine and sodium nitrite to obtain diazonium salt, coupling with phenylquinone, and reducing. It can be used to synthesize polyether etherone, which can be coated on the surface of metal used as biological material.
Description
Technical field
The invention belongs to the organic polymer field, particularly 2-(3-p-methoxy-phenyl) Resorcinol and 2-(2, the 5-Dimethoxyphenyl) Resorcinol and side group contain the polymer materials of hydroxyl and their synthetic method.
Background technology
The polyaryletherketone resinoid has excellent thermotolerance, radiation resistance, insulativity and ageing-resistant etc., its excellent physical and mechanical performance, thermal characteristics, electrical property, and chemical property it is widely used in fields such as electronic apparatus, machinery instrument, communications and transportation and aerospace.But the bond properties of commodity polyaryletherketone and metal is poor.
The prior art close with the present invention is a Chinese patent application, and name is called " Resorcinol synthetic that contains the phenylfluoroform side group ", publication number 1312242, open day September 12 calendar year 2001.This patent disclosure a kind of synthetic technology that contains the Resorcinol of phenylfluoroform side group, with m-trifluoromethyl aniline and benzoquinones is that raw material is synthesized, this monomer not only contains fluorine element but also contain the bigger trifluoromethyl benzene lateral group of volume, utilize this new monomer and 4, the polyaryletherketone that 4 '-difluoro benzophenone synthesizes has lower specific inductivity and solvability preferably.But institute's synthetic monomeric products can't be used for the good polymkeric substance of bond properties synthetic and metal.
Summary of the invention
The technical problem that the present invention solves is that synthesizing methoxy phenyl Resorcinol monomer is used for the polyaryletherketone base polymer that synthetic side group contains hydroxyl, introduces alkoxyl group as binding property functional group, increases the surface adhesion of polymkeric substance.
Methoxyphenyl hydroquinone's monomer of the present invention is 2-(3-p-methoxy-phenyl) Resorcinol or 2-(2, the 5-Dimethoxyphenyl) Resorcinol.
2-of the present invention (3-p-methoxy-phenyl) Resorcinol and 2-(2, the 5-Dimethoxyphenyl) Resorcinol compound structure is respectively:
Methoxyphenyl hydroquinone's synthetic method is to be that the reaction of raw material and Sodium Nitrite generates diazonium salt with the anisidine, then with benzoquinones coupling connection, with the quinone of gained reduce the methoxyphenyl hydroquinone, i.e. biphenol monomer.Concrete is:
The first step reaction is added drop-wise to concentrated hydrochloric acid in the mixture of anisidine and water, is that 2～3.5% sodium nitrite solutions are added drop-wise to above-mentioned reaction system again with concentration, and 0～3 ℃ of temperature of reaction, reaction times are 0.5～2 hour, make diazonium salt.Anisidine, concentrated hydrochloric acid, Sodium Nitrite, water are according to mol ratio 1:3～4:1:10～60.
The reaction of second step in the beaker that mechanical stirring, thermometer are housed or other container, adds benzoquinones, sodium bicarbonate and water.The mol ratio of three and anisidine is 0.6～1.0:3～4:40～60:1.Under constantly stirring, diazonium salt is slowly added.Temperature of reaction is controlled at 9～11 ℃, and the reaction times is 0.5～4 hour, filter the red-purple powder, with behind the distilled water repetitive scrubbing, filtration drying, the benzoquinones that replaces of anisole, productive rate is 80%.
Three-step reaction in churned mechanically there-necked flask is housed, is put into benzoquinones, zinc powder, water, ethanol that anisole replaces, and heated and stirred after the backflow, is added dropwise to hydrochloric acid, reacts 4～6 hours.Heat filtering is separated out green needle-like crystal after the filtrate cooling, and the toluene recrystallization obtains red tabular crystal.Productive rate 80%.The mol ratio of benzoquinones, zinc powder, water, ethanol and hydrochloric acid that anisole replaces is 1:3～4:400～600:40～50:4～6.
Compare with background technology, methoxyphenyl hydroquinone of the present invention is brand-new compound; Methoxyphenyl hydroquinone preparation method of the present invention is different with the mole proportioning of benzoquinones at raw material, raw material, and preferred temperature of reaction.
As methoxyphenyl hydroquinone's application of compound of the present invention, make raw material with the methoxyphenyl hydroquinone, with the reagent of pyridine hydrochloride as the demethylation reaction, the synthetic polyether-ether-ketone that contains the hydroxybenzene replacement.
Contain the synthetic of polyether-ether-ketone that hydroxybenzene replaces, carries out through polycondensation and two processes of demethylation reaction.
At first through the synthetic poly aryl ether ketone polymer that contains the p-methoxy-phenyl replacement of polycondensation:
With methoxyphenyl hydroquinone and 4; 4 '-difluorodiphenyl base ketone is reactant; Anhydrous potassium carbonate is a salt forming agent; N dinethylformamide (DMF) or N,N-DIMETHYLACETAMIDE (DMAC) or tetramethylene sulfone are solvent; toluene or dimethylbenzene are the band aqua; with above-mentioned reactant; salt forming agent; solvent; the band aqua joins mechanical stirring is housed; in the there-necked flask of thermometer; nitrogen protection; being heated to the band aqua begins to reflux; keep temperature to take the water that produces in the reaction out of; Deng aquifer yield reach theoretical value after (theoretical value is identical with the mole number that the methoxyphenyl hydroquinone adds); unnecessary band aqua is steamed; under the solvent refluxing state, reacted 4 hours again, obtain polymkeric substance.Methoxyphenyl hydroquinone, 4, molar ratio scope 0.995～1:0.995～1:1.1～1.2 of 4 '-difluorodiphenyl base ketone, Anhydrous potassium carbonate, the content of band aqua is generally 30%～50% of solvent.In thick product impouring water, filter, solid is directly boiled, filters with methyl alcohol, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain refining polymkeric substance anisole and replace polyether-ether-ketone.
Again through the synthetic polyether-ether-ketone that contains the hydroxyl replacement of demethylation reaction:
Pyridine is joined in the there-necked flask that mechanical stirring, thermometer are housed, stir, under the nitrogen protection concentrated hydrochloric acid is added drop-wise in the pyridine, the mol ratio of the two is 1:1～1.2, and the reaction times is 0.5 hour.Heat temperature raising constantly has water to steam, and when temperature of reaction reaches 210 ℃, keeps temperature 4～5 hours.Be cooled to 180 ℃ then, anisole replaced polyether-ether-ketone join above-mentioned reaction system, reacted 15 hours, just obtain the polyether-ether-ketone that hydroxybenzene replaces.The polyaryletherketone that p-methoxy-phenyl replaces and the mass ratio of pyridine are 1:20～30.Filter, pulverize, nitrogen protection is used hot water wash down, filters, and repeats vacuum drying 3 times.Just obtain containing the polyether-ether-ketone that hydroxyl replaces.
The structure that contains the polyether-ether-ketone that hydroxybenzene replaces that obtains through aforesaid method is, when p-methoxy-phenyl to benzene
When the diphenol raw material used m-anisidine, the structure of the polyether-ether-ketone that contains the hydroxyl replacement that obtains was:
N=70～120 wherein.
When methoxyphenyl hydroquinone's raw material use 2, during the 5-dimethoxyaniline, the hydroxyl that contains that obtains replaces
The structure of polyether-ether-ketone be
N=70～120 wherein.
Of the present invention two kinds of new methoxyphenyl hydroquinone's monomers are disclosed, and with the polyetherketone base polymer of methoxyphenyl hydroquinone's synthesis modification.The present invention introduces methoxyl group and hydroxyl as polarity group, makes polymkeric substance that good binding property be arranged.This polymkeric substance can be applied to the overlay coating such as the metallic substance that uses in the biomaterial, can widen the Application Areas of polymkeric substance.
Description of drawings
Fig. 1 is the mass spectrum of 2-of the present invention (2, the 5-Dimethoxyphenyl) Resorcinol compound.
Fig. 2 is the hydrogen spectrogram at the phenyl ring place of 2-of the present invention (2, the 5-Dimethoxyphenyl) Resorcinol compound.
Fig. 3 is the color atlas of 2-of the present invention (2, the 5-Dimethoxyphenyl) Resorcinol compound.
Embodiment
Embodiment 1: the process of Synthetic 2-(2, the 5-Dimethoxyphenyl) Resorcinol
The first step adds between 77g (0.5mol) 2,5-dimethoxyaniline and H in the beaker that mechanical stirring, thermometer are housed or other container
2O180ml drips HCl180ml (1.5mol), reacts 30min under constantly stirring, and temperature of reaction is controlled at 0 ℃.With 34.5g (0.5mol) NaNO
2Be dissolved in 100ml H
2Among the O, this solution slowly is added dropwise in the reaction system of above-mentioned continuous stirring, temperature of reaction is controlled at 0 ℃, reacts 1 hour.
In second step, in another beaker that mechanical stirring, thermometer are housed or other similar containers, add 43g (0.4mol) benzoquinones, 126g (1.5mol) NaHCO
3With 500ml H
2O under continuous condition of stirring, slowly adds above-mentioned reaction solution, and temperature of reaction is controlled at 10 ℃, reaction times is 2 hours, with the reaction solution suction filtration, obtains red-purple powder (2, the benzoquinones that 5 dimethoxy benzenes replace), carry out drying behind the water repetitive scrubbing, productive rate is 90%.
The 3rd step is with the above-mentioned red-purple powder 61g (0.25mol) that makes, Zn powder 65g (1mol), 1800mlH
2O and 180 milliliters of ethanol add in the 3000ml three-necked bottle, and heated and stirred refluxes, and drips HC150ml, after dropwising, continue reaction 4 hours, heat filtering at once then, the filtrate cooling forms green crystal, after the drying, the toluene recrystallization, drying gets the light red tabular crystal.
The process of above-mentioned Synthetic 2-(2, the 5-Dimethoxyphenyl) Resorcinol can show with reaction formula is generalized.
The 3rd step of second step of the first step.
Can conclude on the mass spectrum that provides from Fig. 1 that embodiment 1 is resulting to be biphenol monomer of the present invention, that is, and 2-(2, the 5-Dimethoxyphenyl) Resorcinol.In the hydrogen spectrogram of Fig. 2 six position correspondences of 1,2,3,4,5,6 are biphenol monomer benzene ring hydrogens of the present invention.Fig. 3 has provided the purity of biphenol monomer of the present invention.
Embodiment 2: the process of Synthetic 2-(3-p-methoxy-phenyl) Resorcinol
Preparation process is with embodiment 1, and with 2, the 5-dimethoxyaniline changes m-anisidine 61g (0.5mol) into, reacts 0 ℃ of temperature of reaction, 1 hour reaction times with Sodium Nitrite under constantly stirring.In being housed, another beaker of mechanical stirring, thermometer adds 43g (0.4mol) benzoquinones, 126g (1.5mol) NaHCO
3With 500ml H
2In the O reaction system, temperature of reaction is controlled at 10 ℃ of reactions 2 hours.Suction filtration obtains the atropurpureus powder, the water repetitive scrubbing, after carry out drying, productive rate is about 90%.Obtain the Resorcinol that meta-methoxy benzene replaces at last, productive rate is 80%.
The 3rd step of second step of the first step.
Embodiment 3: Synthetic 2, the process (1) of the polyether-ether-ketone that the 5-dihydroxy-benzene replaces
With 2; 5-Dimethoxyphenyl Resorcinol 3.69g, Anhydrous potassium carbonate 2.27g, tetramethylene sulfone 20mL, toluene 200mL and 4; 4 '-difluorodiphenyl base ketone 2.7g joins in the there-necked flask that mechanical stirring, thermometer are housed; nitrogen protection; being heated to toluene begins to reflux; after refluxing two hours, do not have water to steam after, emit toluene.Reacted 4 hours down at 206 ℃ again, obtain polymkeric substance.In thick product impouring water, filter, solid is directly boiled, filters with methyl alcohol, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain refining homopolymer---2, the polyether-ether-ketone that the 5-dimethoxy benzene replaces.Reaction formula is as follows:
In the 250ml there-necked flask of mechanical stirring, thermometer is housed, add the 72ml pyridine, constantly stir down, the 80ml concentrated hydrochloric acid is dripped, keep temperature of reaction not above 110 ℃.Heating kept four hours when temperature reaches 210 ℃.Be cooled to 180 ℃, add 2, the polyether-ether-ketone 3g that the 5-dimethoxy benzene replaces reacted 15 hours, was cooled to 120 ℃; discharging is filtered in frozen water, boils with hot water under the nitrogen protection, filters; repeat 3～4 times, oven dry is 2 to white polymer, the polyether-ether-ketone that the 5-dihydroxy-benzene replaces.Reaction formula is as follows:
Embodiment 4: Synthetic 2, the process (2) of the polyether-ether-ketone that the 5-dihydroxy-benzene replaces
With 2; 5-Dimethoxyphenyl Resorcinol 3.69g, Anhydrous potassium carbonate 2.27g, N,N-DIMETHYLACETAMIDE 20mL, toluene 200mL and 4; 4 '-difluorodiphenyl base ketone 3.27g joins in the there-necked flask that mechanical stirring, thermometer are housed; nitrogen protection; being heated to toluene begins to reflux; after refluxing two hours, do not have water to steam after, refluxed 4 hours.Other is with embodiment 3.
Embodiment 5: the process of the polyether-ether-ketone that hydroxybenzene replaces between synthetic
With 2 in embodiment 3 or 4,5-Dimethoxyphenyl Resorcinol changes the m-methoxyphenyl Resorcinol into, and other obtains refining homopolymer---the polyether-ether-ketone that meta-methoxy benzene replaces with embodiment 3 or 4.
Reaction formula is as follows:
With 2 in embodiment 3 or 4, the polyether-ether-ketone that the 5-dimethoxy benzene replaces changes the polyether-ether-ketone that meta-methoxy benzene replaces into, and other obtains the polyether-ether-ketone that a hydroxybenzene replaces with embodiment 3 or 4.Reaction formula is as follows:
Claims (5)
1, a kind of methoxyphenyl hydroquinone's compound is characterized in that, said methoxyphenyl hydroquinone is 2-(2, a 5-Dimethoxyphenyl) Resorcinol, and compound structure is:
2, a kind of synthetic method of methoxyphenyl hydroquinone's compound, be to be that the reaction of raw material and Sodium Nitrite generates diazonium salt with the anisidine, then with benzoquinones coupling connection, with the quinone of gained reduce the methoxyphenyl hydroquinone, it is characterized in that, said anisidine is 2, the 5-dimethoxyaniline; Generate 0～3 ℃ of diazonium salt temperature of reaction; In benzoquinones coupling connection, benzoquinones: sodium bicarbonate: water: the mol ratio of anisidine is 0.6～1.0: 3～4: 40～60: 1, and temperature of reaction is at 9～11 ℃.
3, a kind of methoxyphenyl hydroquinone's application of compound is characterized in that, makes raw material with 2-(2, the 5-Dimethoxyphenyl) Resorcinol, with the reagent of pyridine hydrochloride as the demethylation reaction, and the synthetic polyether-ether-ketone that contains the hydroxybenzene replacement.
4, according to the described methoxyphenyl hydroquinone's application of compound of claim 3, it is characterized in that, contain the synthetic of polyether-ether-ketone that hydroxybenzene replaces, carries out through polycondensation and two processes of demethylation reaction;
Said polycondensation is, with 2-(2, the 5-Dimethoxyphenyl) Resorcinol and 4,4 '-difluorodiphenyl base ketone is reactant, Anhydrous potassium carbonate is a salt forming agent, NN-dimethyl formamide or N,N-DIMETHYLACETAMIDE or tetramethylene sulfone are solvent, toluene or dimethylbenzene are the band aqua, with above-mentioned reactant, salt forming agent, solvent, the band aqua joins mechanical stirring is housed, in the there-necked flask of thermometer, nitrogen protection, being heated to the band aqua begins to reflux, keep temperature to take the water that produces in the reaction out of, after reaching theoretical value Deng aquifer yield, unnecessary band aqua is steamed, under the solvent refluxing state, reacted 4 hours again, obtain polymkeric substance; 2-(2, the 5-Dimethoxyphenyl) Resorcinol, 4, the molar ratio scope 0.995～1: 0.995～1: 1.1～1.2 of 4 '-difluorodiphenyl base ketone, Anhydrous potassium carbonate, the content of band aqua is 30%～50% of solvent; In thick product impouring water, filter, solid is directly boiled, filters with methyl alcohol, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain refining polymkeric substance anisole and replace polyether-ether-ketone;
Said demethylation reacts, and pyridine is joined in the there-necked flask that mechanical stirring, thermometer are housed, and stirs, and under the nitrogen protection concentrated hydrochloric acid is added drop-wise in the pyridine, and the mol ratio of the two is 1: 1～1.2, and the reaction times is 0.5 hour; Heat temperature raising constantly has water to steam, and when temperature of reaction reaches 210 ℃, keeps temperature 4～5 hours; Be cooled to 180 ℃ then, anisole replaced polyether-ether-ketone join above-mentioned reaction system, reacted 15 hours, obtain the polyether-ether-ketone that hydroxybenzene replaces; The polyaryletherketone that p-methoxy-phenyl replaces and the mass ratio of pyridine are 1: 20～30.
According to claim 3 or 4 described methoxyphenyl hydroquinone's application of compound, it is characterized in that 5, methoxyphenyl hydroquinone's raw material uses 2-(2, the 5-Dimethoxyphenyl) Resorcinol, the structure of the polyether-ether-ketone that contains the hydroxyl replacement that obtains is:
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| CN101463186B (en) * | 2008-12-30 | 2011-01-26 | 吉林大学 | Composite type proton conduction membrane material containing amino-sulfonic group and preparation thereof |
| CN101463128B (en) * | 2008-12-30 | 2011-12-07 | 吉林大学 | Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same |
| JP6769075B2 (en) * | 2016-03-31 | 2020-10-14 | 日立化成株式会社 | Aromatic polyketone, method for producing an aromatic polyketone, an aromatic polyketone composition, an aromatic polyketone film, a base material with an aromatic polyketone film, an optical element, an image display device and a coating material. |
| CN106700075B (en) * | 2017-01-23 | 2019-07-23 | 吉林大学 | A kind of side chain has polyarylether, preparation method and its application in terms of seperation film of alcoholic extract hydroxyl group |
| CN107619474B (en) * | 2017-10-18 | 2020-08-11 | 江苏苏博特新材料股份有限公司 | Methoxy polyether derivative, aminated polyether thereof, phosphorylation product thereof, preparation method and application |
| CN114889247A (en) * | 2022-05-07 | 2022-08-12 | 鼎圭新材料科技(上海)有限公司 | Aluminum foil for packaging high-temperature-resistant battery and production process thereof |
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| Synthesis and characterization of poly(aryl ether ketone)s withmethoxyl pendant groups. Li, Aize, Jin, Yuhui, Jiang, Zhenhua.Polymer Preprints,Vol.45 No.1. 2004 |
| Synthesis and characterization of poly(aryl ether ketone)s withmethoxyl pendant groups. Li, Aize, Jin, Yuhui, Jiang, Zhenhua.Polymer Preprints,Vol.45 No.1. 2004 * |
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