CN106279085A - A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride - Google Patents
A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride Download PDFInfo
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- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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Abstract
The invention provides a kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride, comprise the following steps: a) under pressurization and heating condition, the double phthalimide solid of mixing isomery N phenyl N ' phenyl bis ether hydrolyzes in alkaline aqueous solution, generates water-oil phase mixed liquor；After separating oil phase, after dehydration cooling, obtain pasty state solidliquid mixture；B) in the pasty state solidliquid mixture that step a) obtains, add mineral acid, obtain the mixing isomery bis ether tetracarboxylic acid colloid solution of thickness；In colloid solution, add organic acid, make the thickness float in colloid solution be separated into powder float；C) in the powder float that step b) obtains, weak water-soluble solvent is added, system is heated, removing water and the middle organic acid added of step b), the salt in heat filtering removing system, obtain the solid precipitate containing mixing isomery bis ether tetracarboxylic acid dianhydride after filtrate cooling completely.
Description
Technical field
The present invention relates to bis ether tetracarboxylic acid dianhydride synthetic technology, be specifically related to mix the synthesis of isomery bis ether tetracarboxylic acid dianhydride
Method, belongs to bis ether tetracarboxylic acid dianhydride synthesis technical field.
Background technology
Bis ether tetracarboxylic acid dianhydride is a kind of important intermediate of synthesis special material polyimides.Use bis ether tetracarboxylic acid two
Polyimide material prepared by acid anhydride has the feature such as high tenacity, high intensity, can use at 230 DEG C for a long time.
US publication US5068353 describes the synthetic method of a kind of bis ether tetracarboxylic acid dianhydride；China is open specially
Profit CN104529966A the most individually describes the preparation method of preparation 3,3 ', 4,4 '-bisphenol-A bis ether tetracarboxylic acid dianhydride.Above-mentioned
In publication introduce method approximately as:
The double phthalimide of N-phenyl-N '-phenyl-bis ether is acidified after ordinary-pressure hydrolysis again, obtains water-fast double
Ether tetracarboxylic acid solid；
Bis ether tetracarboxylic acid solid is obtained bis ether tetracarboxylic acid dianhydride after thermal dehydration；
Its synthetic route reaction equation is as follows:
Wherein, R represents aromatic hydrocarbyl, as Deng；X represents K, Na etc.
Bis ether tetracarboxylic acid dianhydride has three kinds of isomers, is 3 respectively, and 3 ', 4,4 '-bis ether tetracarboxylic acid dianhydride, 2,3 ', 3,4 '-
Bis ether tetracarboxylic acid dianhydride and 2,2 ', 3,3 '-bis ether tetracarboxylic acid dianhydride, the molecular formula of three kinds of isomers is as follows:
3,3 ', 4,4 '-bis ether tetracarboxylic acid dianhydride
2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride
2,2 ', 3,3 '-bis ether tetracarboxylic acid dianhydride
Theoretical according to materials synthesis, if these three isomer is used in mixed way, as preparing the raw material of polyimides, that
Prepared polyimides can have higher vitrification point, but has relatively low glutinous stream temperature, and this allows for isomery
Polyimides has more resistant to high temperature and the feature of easier machine-shaping, therefore, and the mixing isomery bis ether that three kinds of isomers coexist
The study on the synthesis of tetracarboxylic acid dianhydride becomes the study hotspot of polyimides academia.
But in mixing isomery bis ether tetracarboxylic acid dianhydride building-up process, it is found that many problems:
One, the double phthalimide of mixing isomery N-phenyl-N '-phenyl-bis ether have three kinds of isomers, when basic hydrolysis only
Have a kind of isomer can with complete hydrolysis, and other two isomer at short notice can not complete hydrolysis, need heating at least 200
Could hydrolyze more than hour completely；
Its two, mixing isomery bis ether tetracarboxylic acid aqueous solution of alkali metal salt through steam water, acidifying after, obtain is that one dissolves in
The colloid solution of the mixing isomery bis ether tetracarboxylic acid of water, therefore cannot obtain bis ether tetracarboxylic acid solid.
Its three, bis ether tetracarboxylic acid solid in atmosphere, in a vacuum thermal dehydration formed during dianhydride, be dehydrated slower
And blackout apt to deteriorate；In acetic anhydride, dehydrating effect is preferable, but can have certain corrosion, and acetic acid to equipment when being dried solvent
Acid anhydride belongs to control chemicals, can bring unnecessary trouble in course of industrialization.
There is the existence of one, 2 two difficult points, cause mixing the progress of the synthesis of isomery bis ether tetracarboxylic acid dianhydride almost
Stay cool, up to the present there is not yet 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride or containing 2,3 ', 3,4 '-bis ether tetramethyl
The report that the product of acid dianhydride mixing isomery bis ether tetracarboxylic acid dianhydride is synthesized.
Accordingly, it would be desirable to develop a kind of new synthetic method, successfully prepare containing 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride
The product of mixing isomery bis ether tetracarboxylic acid dianhydride.
Summary of the invention
For mixing isomery bis ether tetracarboxylic acid dianhydride produced problem in synthesis, the purpose of the present invention aims to provide one
The preparation method of mixing isomery bis ether tetracarboxylic acid dianhydride, after the double phthalimide hydrolysis of mixing isomery N-phenyl-N '-phenyl-bis ether
Introducing organic acid is as dispersant, and realizes effectively dehydration by the addition of weak water-soluble solvent, thus it is different successfully to prepare mixing
Structure bis ether tetracarboxylic acid dianhydride solid.
In order to realize above goal of the invention, technical scheme is as follows:
A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride, comprises the following steps:
A) under pressurization and heating condition, the double phthalimide solid of mixing isomery N-phenyl-N '-phenyl-bis ether is in alkalescence
Aqueous solution hydrolyzes, generates bis ether tetracarboxylic acid saline solution and the water-oil phase mixed liquor of aniline；After separating oil phase, heated aqueous
Steam the water of partial volume, after cooling, obtain pasty state solidliquid mixture；
B) in the pasty state solidliquid mixture that step a) obtains, add mineral acid, obtain the mixing isomery bis ether tetramethyl of thickness
Acid colloids solution；In colloid solution, add organic acid, make the thickness float in colloid solution be separated into powder float；
C) in the powder float that step b) obtains, add weak water-soluble solvent, system is heated, removes water completely
With the organic acid added in step b), the salt in heat filtering removing system, obtain containing 2,3 ' after filtrate cooling, 3,4 '-different
The solid precipitate of the mixing isomery bis ether tetracarboxylic acid dianhydride of structure body.
Present invention additionally comprises step d), the filter cake that the pressed powder precipitate obtained by step c) is filtrated to get carries out vacuum
Being dried, dried solid after crushed, obtains mixing isomery bis ether tetracarboxylic acid dianhydride product.
In the present invention, in step a), the double phthalimide of described mixing isomery N-phenyl-N '-phenyl-bis ether is carbon number
The double phthalimide of the mixing isomery bis ether of 34 to 43, includes but not limited to: the N-phenyl-N '-phenyl-triphen containing three kinds of isomers
The double phthalimide of diether, the double phthalimide of N-phenyl-N '-phenyl-bisphenol-A diether containing three kinds of isomers or containing three kinds of isomers
The double phthalimides of N-phenyl-N '-phenyl-'-biphenyl diphenol diether etc..
In the present invention, three kinds of isomers of the double phthalimide of described mixing isomery N-phenyl-N '-phenyl-bis ether are respectively
The double phthalimide of 3,3 ', 4,4 '-N-phenyl-N '-phenyl-bis ether, the double phthaloyl of 2,3 ', 3,4 '-N-phenyl-N '-phenyl-bis ether are sub-
Amine and 2, the double phthalimide of 2 ', 3,3 '-N-phenyl-N '-phenyl-bis ether, wherein 2,3 ', 3,4 '-N-phenyl-N '-phenyl-bis ether
The content of double phthalimides is between 20-55wt%, preferably 35-55wt%, more preferably 50-55wt%, based on mixing isomery N-
The gross weight of the double phthalimide of phenyl-N '-phenyl-bis ether, other two kinds of isomers can be combined with arbitrary proportion.
In step a) of the present invention, described alkaline aqueous solution includes sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution, excellent
Select sodium hydrate aqueous solution.
In step a) of the present invention, the double phthalimide of described mixing isomery N-phenyl-N '-phenyl-bis ether and alkaline aqueous solution
In the mol ratio of alkali be 1:4 to 1:6, preferably 1:5-1:5.5.
In step a) of the present invention, described pressure (gauge pressure) is 0.5-0.7MPa, preferably 0.6-0.65MPa；Described add
The temperature of heat is 155-170 DEG C, preferably 160-165 DEG C.Hydrolysis time is 5-8 hour, preferably 6-7 hour.
In step a) of the present invention, the double phthalimide solid of mixing isomery N-phenyl-N '-phenyl-bis ether is at alkaline water
When in solution, hydrolysis starts, the mol ratio of the double phthalimide of described N-phenyl-N '-phenyl-bis ether and water is 1:7-1:12, preferably
1:9-1:10。
After step a) of the present invention separates oil phase, heated aqueous steams the water of 50-70% volume, overall based on aqueous phase
Long-pending, obtain pasty state solidliquid mixture after being then cooled to room temperature.
In described step b), add mineral acid be acidified, described mineral acid be mass concentration be the hydrochloric acid of 30-37%.
In the present invention, the alkalescence that in the mineral acid added in step b), free hydrionic integral molar quantity adds with step a)
The ratio of the mole of the hydroxide ion in aqueous solution is 1.5:1-2:1, preferably 1.7:1-1.8:1.
In the present invention, step b) adds in colloid solution organic acid under agitation, peptizaiton can be played,
Described organic acid is formic acid and/or acetic acid, and addition is to mix the double phthalein of isomery N-phenyl-N '-phenyl-bis ether described in step a)
The 5-15wt% of acid imide quality, preferably 6-10wt%.
In the present invention, in described step c), described 20 DEG C of dissolubility in water of weak water-soluble solvent want 0.05-2.4g/
100g；Between boiling point is 130-181 DEG C, between preferably 152-173 DEG C.Preferably, described weak water-soluble solvent includes that ketone is molten
One or more in agent；It is highly preferred that described weak water-soluble solvent includes but not limited to Ketohexamethylene, methyln-hexyl ketone, cycloheptanone, 3-
One or more in octanone and Ketocyclopentane etc..
Under agitation system is heated after step c) of the present invention adds weak water-soluble solvent, carry out dehydration, reaction
Temperature is the boiling temperature of weak water-soluble solvent, the water in removing system and the middle organic acid added of step b), dehydration
Time is 5-12 hour, preferably 7-9 hour.The addition of weak water-soluble solvent is the mixing isomery N-benzene added in step a)
8-12 times of the double phthalimide quality of base-N '-phenyl bis ether, preferably 9-10 times.
Owing to water and weak water-soluble solvent dissolubility are the best, therefore when solvent refluxing, water and solvent azeotropic, condensed
After, water and solvent are layered in water knockout drum, owing in the present invention, water is bigger than the density of described weak water-soluble solvent, therefore water under
Layer.Meanwhile, mixing isomery bis ether tetracarboxylic acid can be dehydrated into anhydride reactant in a solvent, therefore when solvent refluxing, and mixing
The water that isomery bis ether tetracarboxylic acid is taken off discharges system the most simultaneously.
In the present invention, after step c) removes organic acid completely that add in water and step b), carry out heat filtering, maintain heat
The temperature filtered is identical with dehydration temperature, i.e. heat filtering temperature is identical with the boiling temperature of weak water-soluble solvent, to remove
Salt in system.
In the present invention, the filtrate after heat filtering is cooled to-10 to 80 DEG C by step c), after filtrate cooling, according to cooling
Rear different temperature, can obtain the mixing isomery bis ether tetramethyl of different proportion of composing in filter cake the most after filtration and filtrate
Acid dianhydride.
As the preferred scheme of one, first cool the filtrate to 70-80 DEG C, filter, leach containing 3,3 ', 4,4 '-
Bis ether tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-bis ether tetracarboxylic acid dianhydride and 2,3 ', the three kinds of isomers of 3,4 '-bis ether tetracarboxylic acid dianhydride
Pressed powder, wherein 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride content is at 11-15wt%, based on three kinds of isomer solid powder
Gross weight；Being cooled to residual filtrate at-10 to 0 DEG C filter again, obtain 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride content is at 75-
The bis ether tetracarboxylic acid dianhydride solid of three kinds of isomer mixing of 87wt%, the three kinds of isomers obtained after filtering based on residual filtrate
The gross weight of the bis ether tetracarboxylic acid dianhydride of mixing.
Or, as the preferred scheme of another kind, directly filtrate is down to-10 to 0 DEG C, leaches dianhydride solid, obtain and step
Three kinds of identical mixing of isomer proportion in rapid a) the middle double phthalimide of the raw material mixing isomery N-phenyl-N '-phenyl-bis ether added
Close isomery bis ether tetracarboxylic acid dianhydride.
In the present invention, the pressed powder precipitate containing mixing isomery bis ether tetracarboxylic acid dianhydride obtained in step c) passes through
Vacuum drying, described vacuum drying temperature is 110-170 DEG C, preferably 140 to 150 DEG C.Described vacuum is-0.098MPa
To-0.1MPa.Described two step drying times are 5-12 hour, preferably 7-9 hour.
The inventive method can realize feed stock conversion and reach 97-99.5%, product yield 93-95%, three kinds of isomers two
Total purity of acid anhydride can reach more than 98.5wt%.
Beneficial effects of the present invention is as follows:
1, solve mixing isomery bis ether tetracarboxylic acid to be dissolved in water and cannot obtain mixing isomery bis ether tetracarboxylic acid dianhydride solid
Problem；
2, by controlling the difference of filtration temperature, it is possible to obtain the bis ether tetracarboxylic acid dianhydride of different isomer composition.
Accompanying drawing explanation
Fig. 1 is mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride HPLC spectrogram after aniline processes
Fig. 2 is the HPLC spectrogram of mixing isomery '-biphenyl diphenol diether tetracarboxylic acid colloid solution
Detailed description of the invention
Embodiment 1
The synthesis of mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride
565.2g water, 62.8g mixing isomery N-phenyl-N '-phenyl-biphenyl two is added in the compressive reaction still of 1000ML
(with water quality ratio for 1:9, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaloyls are sub-for the double phthalimide of phenol diether
Amine and 3,3 ', the mass ratio that ratio is three of 4,4 '-bis-phthalimides is 1:2:2), the sodium hydroxide (20g) of 0.5mol, will
Reactor seals, and opens stirring, is 0.6MPa, now reactor temperature by temperature up to reactor pressure (gauge pressure, lower same)
It is about 160 DEG C, after reacting 7 hours, stops heat drop to room temperature.Open reactor, reactant liquor is taken out, divides upper strata with separatory funnel
Oily aniline.Remaining liquid is equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating,
Steam the water of about 60% volume, after cooling, become pasty state.
The hydrochloric acid 103ml (being equivalent to pure hydrogen chloride 0.85mol) that concentration is 30wt% is added in the liquid/paste obtained,
The colloid solution of celadon thickness is formed in there-necked flask.In bottle, add the acetic acid of 3.14g, bottle occurring, solid separates out.
In reaction bulb, add 670g Ketohexamethylene (2.4g/100g, boiling point 152 DEG C during the dissolubility in water 20 DEG C), stir
Mix lower heating.When temperature rises to about 152 DEG C during i.e. Ketohexamethylene boiling point, the acid steamed gradually is carried over reaction system.When dividing
When occurring without the globule in hydrophone, illustrating that reaction terminates, it is complete that three kinds of '-biphenyl diphenol diether tetracarboxylic acids are all dehydrated into acid anhydride.Reaction is about
Need 7 hours.
Solidliquid mixture is filtered while hot.Filtrate is cooled to 0 DEG C.Will separate out solid continue filter, filter cake-
0.098MPa, it is dried 7 hours at 145 DEG C, solid is pulverized, obtains mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride.
Three kinds of content of isomer of the above-mentioned mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride prepared analyze process such as
Under: take 0.03g sample and add 20ml chromatographically pure level N-Methyl pyrrolidone, after dissolving under slight fever stirs, add accurate weighing
High-purity aniline of two times of moles of dianhydride sample, after stirring 10 minutes, makes '-biphenyl diphenol diether tetracarboxylic acid dianhydride react completely and turns
Turn to the double phthalimide of N-phenyl-N '-phenyl-'-biphenyl diphenol diether of corresponding isomer, then by solution chromatographically pure level first
Base ketopyrrolidine is diluted to 100ml, carries out liquid-phase chromatographic analysis after shaking up, and flow phase: acetonitrile/water=67/33 (volume ratio)；Stream
Speed 1.0ml/min；UV detector, wavelength 254nm；C18 chromatographic column, chromatogram is shown in Fig. 1.
According to chromatographic results analysis and be scaled the content of corresponding '-biphenyl diphenol diether tetracarboxylic acid dianhydride isomer respectively
For: 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4,4 '-isomer mass ratio is 1:2:2；Three kinds different
Structure body purity summation is 99.0%, and yield is 92%.
Embodiment 2
The synthesis of mixing isomery triphen diether tetracarboxylic acid dianhydride
552g water, 55.2g mixing isomery N-phenyl-N '-phenyl-'-biphenyl diphenol is added in the compressive reaction still of 1000ML
The double phthalimide of diether (it is 1:10 with the mass ratio of water, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaloyls Asia
Amine and 3,3 ', the mass ratio of 4,4 '-bis-phthalimide threes is 1:2:1), the sodium hydroxide (24g) of 0.6mol, by reactor
Sealing, open stirring, be 0.7MPa by temperature up to reactor pressure, now reactor temperature is about 167 DEG C, and reaction 8 is little
Shi Hou, stops heat drop to room temperature.Open reactor, reactant liquor is taken out, divides the oily aniline on upper strata with separatory funnel.Will residue
Liquid be equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating, steam about 70% volume
Water, after steaming water, becomes pasty state after cooling.
In the liquid/paste obtained, add hydrochloric acid about the 101ml that concentration is 37% (be equivalent to pure hydrogen chloride
1.2mol), the colloid solution of celadon thickness is formed in there-necked flask.In bottle, add the acetic acid of 8.28g, bottle occurring, solid is analysed
Go out.
662.4g2-octanone (0.09g/100g, boiling point 173 DEG C during the dissolubility in water 20 DEG C) is added in reaction bulb,
The lower heating of stirring.When temperature rises to about 173 DEG C of i.e. methyln-hexyl ketone boiling points, the acid steamed gradually is carried over reaction system.When dividing
When occurring without the globule in hydrophone, illustrating that reaction terminates, it is complete that three kinds of triphen diether tetracarboxylic acids are all dehydrated into acid anhydride.Reaction takes around
5 hours.It is down to room temperature.
Solidliquid mixture is filtered while hot.Filtrate is cooled to-10 DEG C.Will separate out solid continue filter, filter cake-
0.099MPa, it is dried 12 hours at 140 DEG C, solid is pulverized, obtains mixing isomery triphen diether tetracarboxylic acid dianhydride.Through dividing
Analysis, 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4,4 '-isomer mass ratio is 1:2:1, and three kinds are different
Structure body purity summation is 99.0%, and yield is 91.5%.
Embodiment 3
The synthesis of mixing isomery bisphenol-A diether tetracarboxylic acid dianhydride
The compressive reaction still of 1000ML adds 469g water, 67g (altogether 0.1mol) mixing isomery N-phenyl-N '-phenyl-
The double phthalimide of bisphenol-A diether (it is 1:7 with the mass ratio of water, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaleins
Acid imide and 3,3 ', the mass ratio of 4,4 '-bis-phthalimide threes is 15:55:30), the sodium hydroxide (16g) of 0.4mol,
Being sealed by reactor, open stirring, be 0.5MPa by temperature up to reactor pressure, now reactor temperature is about 155 DEG C,
After reacting 5 hours, stop heat drop to room temperature.Open reactor, reactant liquor is taken out, divides the oily benzene on upper strata with separatory funnel
Amine.Remaining liquid is equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating, steams about
The water of 60% volume, about remains 240ml thick liquid after steaming water, becomes pasty state after cooling.
Hydrochloric acid about the 67ml (being equivalent to pure hydrogen chloride 0.6mol) that concentration is 30% is added in the liquid/paste obtained,
The colloid solution of celadon thickness is formed in there-necked flask.In bottle, add the formic acid of 4.02g, bottle occurring, solid separates out.
In reaction bulb, add the cycloheptanone (0.15g/100g, boiling point 181 during the dissolubility in water 20 DEG C) of 603g, stir
Mix lower heating.When temperature rises to about 181 DEG C of i.e. cycloheptanone boiling points, the acid steamed gradually is carried over reaction system.When a point water
When occurring without the globule in device, illustrating that reaction terminates, it is complete that three kinds of bisphenol-A diether tetracarboxylic acids are all dehydrated into acid anhydride.Reaction takes around
12 hours.
Solidliquid mixture is filtered while hot.Filtrate is cooled to-5 DEG C, will separate out solid continue filter, filter cake-
0.098MPa, it is dried 8 hours at 140 DEG C, solid is pulverized, obtains mixing isomery triphen diether tetracarboxylic acid dianhydride.Through dividing
Analysis, 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4,4 '-isomer mass ratio is 15:55:30, three kinds
Enantiomeric purity summation is 99.2%, and yield is 93%.
Embodiment 4
The synthesis of mixing isomery resorcinol diether tetracarboxylic acid dianhydride
662.4g water, 55.2g mixing isomery N-phenyl-N '-phenyl-isophthalic two is added in the compressive reaction still of 1000ML
The double phthalimide of phenol diether (it is 1:12 with the mass ratio of water, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaloyls
Imines and 3,3 ', the mass ratio of 4,4 '-bis-phthalimide threes is 10:35:55), the potassium hydroxide (30.8g) of 0.55mol,
Being sealed by reactor, open stirring, be 0.65MPa by temperature up to reactor pressure, now reactor temperature is about 165
DEG C, after reacting 6 hours, stop heat drop to room temperature.Open reactor, reactant liquor is taken out, divides the oily on upper strata with separatory funnel
Aniline.Remaining liquid is equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating, steams about
The water of 50% volume, becomes pasty state after cooling.
In the liquid/paste obtained, add hydrochloric acid about the 83ml that concentration is 37% (be equivalent to pure hydrogen chloride
0.99mol), the colloid solution of celadon thickness is formed in there-necked flask.In bottle, add the acetic acid of 5.52g, bottle occurs solid
Separate out.
The 3-octanone (during the dissolubility in water 20 DEG C 0.82, boiling point 157) of 441.6g is added, under stirring in reaction bulb
Heating.When temperature rises to about 157 DEG C of i.e. 3-octanone boiling points, the acid steamed gradually is carried over reaction system.When in water knockout drum
When occurring without the globule, illustrating that reaction terminates, it is complete that three kinds of resorcinol diether tetracarboxylic acids are all dehydrated into acid anhydride.Reaction takes around 9
Hour.
Solidliquid mixture is carried out filtered while hot desalination.Filtrate is cooled to 80 DEG C, again leaches a part of solid, is designated as solid
Body A；The filtrate filtering solid A continues to be cooled to 0 DEG C, again filters, and a part of solid of getting back is designated as solid B.At 170 DEG C
Under, close under the conditions of absolute pressure, respectively solid A and solid B is dried 9 hours.
Through analyzing: in solid A 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4, the ratio of 4 '-isomer
Example is respectively 8:8:48, and three kinds of enantiomeric purity summations are 99.2%, and 2,3 ', 3,3 '-content of isomer is 12.5%, and yield is
53%.
In solid B 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4, the ratio of 4 '-isomer is respectively
For 2:27:7,2,3 ', 3,3 '-content of isomer is 75%, and three kinds of enantiomeric purity summations are 99.0%, and yield is 40.2%.
Mixing isomery resorcinol diether tetracarboxylic acid dianhydride total recovery is 93.2%.
Embodiment 5
The synthesis of mixing isomery bisphenol S diether tetracarboxylic acid dianhydride
657.4g water, 69.2g mixing isomery N-phenyl-N '-phenyl-bisphenol S is added in the compressive reaction still of 1000ML
The double phthalimide of diether (it is 1:12 with the mass ratio of water, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaloyls Asia
Amine and 3,3 ', the mass ratio of 4,4 '-bis-phthalimide threes is 10:53:37), the potassium hydroxide (29.12g) of 0.52mol,
Being sealed by reactor, open stirring, be 0.63MPa by temperature up to reactor pressure, now reactor temperature is about 163
DEG C, after reacting 6.5 hours, stop heat drop to room temperature.Open reactor, reactant liquor is taken out, divides the oil on upper strata with separatory funnel
Shape aniline.Remaining liquid is equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating, steams
The water of about 60% volume, becomes pasty state after cooling.
In the liquid/paste obtained, add hydrochloric acid about the 90ml that concentration is 37% (be equivalent to pure hydrogen chloride
0.91mol), the colloid solution of celadon thickness is formed in there-necked flask.In bottle, add the formic acid of 5.536g, bottle occurs solid
Separate out.
The Ketocyclopentane (20 DEG C of dissolubility 0.05 in water, boiling point 130 DEG C) of 657.4g is added, under stirring in reaction bulb
Heating.When temperature rises to about 130 DEG C of i.e. Ketocyclopentane boiling points, the acid steamed gradually is carried over reaction system.When in water knockout drum
When occurring without the globule, illustrating that reaction terminates, it is complete that three kinds of bisphenol S diether tetracarboxylic acids are all dehydrated into acid anhydride, and it is little that reaction takes around 8
Time.
Solidliquid mixture is carried out filtered while hot desalination.Filtrate is cooled to 80 DEG C,
Again leach a part of solid, be designated as solid C；The filtrate filtering solid C continues to be cooled to 0 DEG C, again filters, again
Obtain a part of solid, be designated as solid D.At 110 DEG C, under the conditions of-0.098MPa, respectively solid C and solid D is dried 5 little
Time.
Through analyzing: in solid C 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4, the ratio of 4 '-isomer
Example is respectively 8:5:32, and 2,3 ', 3,4 '-content of isomer is 11%, and three kinds of enantiomeric purity summations are 99.2wt%, and yield is
45%.
In solid D 2,2 ', 3,3 '-isomer, 2,3 ', 3,4 '-isomer and 3,3 ', 4, the ratio of 4 '-isomer is respectively
For 2:48:5,2,3 ', 3,4 '-isomer is 87%, and three kinds of enantiomeric purity summations are 99.0%, and yield is 46.2%.
The total recovery of bisphenol S diether tetracarboxylic acid dianhydride is 91.2%.
Comparative example 1
552g water, 55.2g mixing isomery N-phenyl-N '-phenyl-'-biphenyl diphenol is added in the compressive reaction still of 1000ML
The double phthalimide of diether (it is 1:10 with the mass ratio of water, wherein 2,2 ', 3,3 '-bis-phthalimides, 2,3 ', 3,4 '-bis-phthaloyls Asia
Amine and 3,3 ', the ratio of 4,4 '-bis-phthalimides is about 1:2:1), the sodium hydroxide (24g) of 0.6mol, reactor is close
Envelope, opens stirring, is 0.7MPa by temperature up to reactor pressure, and now reactor temperature is about 167 DEG C, reacts 8 hours
After, stop heat drop to room temperature.Open reactor, reactant liquor is taken out, divides the oily aniline on upper strata with separatory funnel.By remaining
Liquid is equipped with in the 2000ml there-necked flask of water knockout drum and ball condenser, normal heating, steams the water of about 70% volume,
After steaming water, after cooling, become pasty state.
In the liquid/paste obtained, add hydrochloric acid about the 101ml that concentration is 37% (be equivalent to pure hydrogen chloride
1.2mol), the colloid solution of celadon thickness is formed in there-necked flask.After colloid solution sampling liquid-phase chromatographic analysis, analyze
Result is Fig. 2, has obtained three peaks, and three components are respectively 2,2 ', 3,3 '-triphen diether tetracarboxylic acid, 2,3 ', 3,4 '-triphen
Diether tetracarboxylic acid and 3,3 ', 4,4 '-triphen diether tetracarboxylic acid, filters colloid solution, it is impossible to obtain solid product.
It is as follows that process analyzed by colloid solution: takes 0.3g solution example and is diluted with water to 100ml, shakes up rear sample introduction.Liquid phase color
Spectral condition is as follows: flowing phase: acetonitrile/1wt% ammonium dihydrogen phosphate aqueous solution=30/70 (volume ratio)；Flow velocity 1.0ml/min；UV
Detector, wavelength 254nm；C18 chromatographic column.
Comparative example 2
657.4g water, 69.2gN-phenyl-N '-phenyl-3,3 is added in the compressive reaction still of 1000ML ', 4,4 '-bis-phenol
S diether double phthalimide (being 1:12 with the mass ratio of water), the potassium hydroxide (29.12g) of 0.52mol, seal reactor, open
Open stirring, by temperature up to 100 DEG C, be now normal pressure in reactor, after reacting 24 hours, stop heat drop to room temperature.Open reaction
Still, takes out reactant liquor, divides the oily aniline on upper strata with separatory funnel.Remaining liquid is equipped with water knockout drum and spherical
In the 2000ml there-necked flask of condenser, normal heating, steam the water of about 60% volume, after cooling, become pasty state.
In the liquid/paste obtained, add hydrochloric acid about the 90ml that concentration is 37% (be equivalent to pure hydrogen chloride
0.91mol), white solid precipitation is formed in there-necked flask.After precipitation being stirred, it is heated to 100 DEG C, is incubated 5 hours.
After insulation terminates, system is down to room temperature, solid is filtered, and after carrying out washing 5 times by filter cake with pure water, will filter
Cake is put in convection oven and is dried 3 hours with 100 DEG C, obtains 3,3 ', 4,4 '-bisphenol S diether tetracarboxylic acid solid.
3 will obtained, 3 ', 4,4 '-bisphenol S diether tetracarboxylic acid adds in 500ml acetic anhydride, after being heated to reflux 2 hours, fall
Temperature by solid filter, by filter cake 100 DEG C ,-0.098MPa be vacuum dried 2 hours, obtain product comprises only after testing isomery
Body 3,3 ', 4,4 '-bisphenol S diether tetracarboxylic acid dianhydride, yield 87.3%, purity 98.3%.
Comparative example 3
Addition 657.4g water, 69.2gN-phenyl-N '-phenyl-2 in the compressive reaction still of 1000ML, 2 ', 3,3 '-bis-phenol
S diether double phthalimide (being 1:12 with the mass ratio of water), the potassium hydroxide (29.12g) of 0.52mol, seal reactor, open
Open stirring, by temperature up to 160 DEG C, be now 0.6MPa in reactor, after reacting 8 hours, stop heat drop to room temperature.Open reaction
Still, takes out reactant liquor, divides the oily aniline on upper strata with separatory funnel.Remaining liquid is equipped with water knockout drum and spherical
In the 2000ml there-necked flask of condenser, normal heating, steam the water of about 60% volume, after cooling, become pasty state.
In the liquid/paste obtained, add hydrochloric acid about the 90ml that concentration is 37% (be equivalent to pure hydrogen chloride
0.91mol), white solid precipitation is formed in there-necked flask.After precipitation being stirred, it is heated to 100 DEG C, is incubated 5 hours.
After insulation terminates, system is down to room temperature, solid is filtered, and after carrying out washing 5 times by filter cake with pure water, will filter
Cake is put in convection oven and is dried 3 hours with 100 DEG C, obtains 2,2 ', 3,3 '-bisphenol S diether tetracarboxylic acid solid.
2 will obtained, 2 ', 3,3 '-bisphenol S diether tetracarboxylic acid adds in 500ml acetic anhydride, after being heated to reflux 5 hours, fall
Temperature by solid filter, by filter cake 100 DEG C ,-0.098MPa be vacuum dried 2 hours, obtain product and comprise only 2,2 ', 3 after testing,
3 '-bisphenol S diether tetracarboxylic acid dianhydride.Yield 89.3%, purity 98.7%.
Comparative example 4
Synthesis of polyimides resin is carried out with reference to " Takekoshi T.J.Polym.Sci, 1967,11:609 " method.
The mixing isomery diether tetracarboxylic acid dianhydride and the 4,4 '-diaminodiphenyl ether that use preparation in embodiment 1 to 3 respectively gather
Close, obtain polyimide resin 1-3.
Using the solid A that obtains of embodiment 4 and solid B respectively with 4,4 '-diaminodiphenyl ether is polymerized, and obtains polyimides
Resin 4-1 and resin 4-2.
Using the solid C that obtains of embodiment 5 and solid D respectively with 4,4 '-diaminodiphenyl ether is polymerized, and obtains polyimides
Resin 5-1 and resin 5-2.
Use 3,3 ', 4,4 '-bisphenol S diether tetracarboxylic acid dianhydride and the 2,2 ', 3 of comparative example 3 preparation of comparative example 2 preparation,
3 '-bisphenol S diether tetracarboxylic acid dianhydride product is respectively with 4, and 4 '-diaminodiphenyl ether is polymerized, and prepares polyimide resin 6 He
The product of resin 7,
The properties of product test result of resin 1-7 refers to table 1.
The properties of product tables of data of table 1 polyimide resin 1-7
Above example is it can be seen that the present invention can prepare 3 kinds of isomers (especially 2,3 ', 3,4 '-isomer) together
Time the mixing diether tetracarboxylic acid dianhydride solid that exists, and use the polyamides of mixing diether tetracarboxylic acid dianhydride synthesis prepared by the present invention
Imide resin has higher vitrification point, lower glutinous stream temperature and bigger molecular weight.
The performance of resin 5-1 and resin 5-2 and resin 6 and resin 7 carries out contrasting it can be seen that owing to preparing resin 5-1
With in the raw materials bisphenol S diether tetracarboxylic acid dianhydride of resin 5-2 containing the 2,3 ', 3 of dissymmetrical structure, 4 '-isomer, with 4,
The performance of the resin obtained after the polymerization of 4 '-diaminodiphenyl ether is superior to resin 6 and resin 7, illustrates containing 2,3 ', 3,4 '-no
The polyimides of symmetrical structure to have the advantage of obvious thermal property and processing characteristics than the polyimides of symmetrical structure.With
Time, the performance of resin 5-1 is good not as the performance of 5-2, but better than the performance of resin 6 and resin 7, in this explanation polyimides 2,
3 ', 3,4 '-dissymmetrical structure unit is the most, and the performance of resin is the best, more has superiority in terms of thermostability and processability.
Claims (11)
1. mix a preparation method for isomery bis ether tetracarboxylic acid dianhydride, comprise the following steps:
A) under pressurization and heating condition, the double phthalimide solid of mixing isomery N-phenyl-N '-phenyl-bis ether is water-soluble in alkalescence
Liquid hydrolyzes, generates bis ether tetracarboxylic acid saline solution and the water-oil phase mixed liquor of aniline；After separating oil phase, heated aqueous steams
The water of partial volume, obtains pasty state solidliquid mixture after cooling；
B) in the pasty state solidliquid mixture that step a) obtains, add mineral acid, obtain the mixing isomery bis ether tetracarboxylic acid glue of thickness
Liquid solution；In colloid solution, add organic acid, make the thickness float in colloid solution be separated into powder float；
C) in the powder float that step b) obtains, add weak water-soluble solvent, system is heated, completely removing water and step
Rapid b) the middle organic acid added, the salt in heat filtering removing system, obtain containing 2,3 ' after filtrate cooling, 3,4 '-isomer
Mixing isomery bis ether tetracarboxylic acid dianhydride solid precipitate.
Preparation method the most according to claim 1, it is characterised in that the organic acid added in colloid solution in step b)
For formic acid and/or acetic acid, addition is to mix the double phthalimide quality of isomery N-phenyl-N '-phenyl-bis ether described in step a)
5-15wt%, preferably 6-10wt%.
Preparation method the most according to claim 1 and 2, it is characterised in that weak water-soluble solvent 20 DEG C described in step c)
Dissolubility in water is 0.05-2.4g/100g；Between boiling point is 130-181 DEG C, between preferably 152-173 DEG C；Preferably,
Described weak water-soluble solvent includes one or more in ketones solvent, it is further preferred that described weak water-soluble solvent include Ketohexamethylene,
One or more in methyln-hexyl ketone, cycloheptanone, 3-octanone and Ketocyclopentane.
4. according to the preparation method described in claim 1 or 3, it is characterised in that the addition of described weak water-soluble solvent is step
8-12 times of rapid a) the middle double phthalimide quality of mixing isomery N-phenyl-the N '-phenyl bis ether added, preferably 9-10 times.
Preparation method the most according to claim 1, it is characterised in that in described step a), described mixing isomery N-phenyl-
The double phthalimide of N '-phenyl-bis ether is the double phthalimide of mixing isomery bis ether of carbon number 34 to 43, selected from containing three kinds of isomeries
The double phthalimide of the N-phenyl-N '-phenyl-triphen diether of body, N-phenyl-N '-phenyl-bisphenol-A diether containing three kinds of isomers
Double phthalimides or the double phthalimide of the N-phenyl-N '-phenyl-'-biphenyl diphenol diether containing three kinds of isomers；Described mixing isomery
The content of the double phthalimide of 2,3 ', 3,4 '-N-phenyl-N '-phenyl-bis ether in the double phthalimide of N-phenyl-N '-phenyl-bis ether
For 20-55wt%, preferably 35-55wt%, more preferably 50-55wt%, based on the double phthalein of mixing isomery N-phenyl-N '-phenyl-bis ether
Imido gross weight.
6. according to the preparation method according to any one of claim 1-5, it is characterised in that in described step a), described alkalescence
Aqueous solution includes sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution, preferably sodium hydrate aqueous solution；Described mixing isomery N-
The mol ratio of the double phthalimide of phenyl-N '-phenyl-bis ether and the alkali in alkaline aqueous solution be 1:4 to 1:6, preferably 1:5 to 1:
5.5。
7., according to the preparation method according to any one of claim 1-5, it is characterised in that in described step a), mix isomery
When the double phthalimide solid of N-phenyl-N '-phenyl-bis ether hydrolyzes beginning in alkaline aqueous solution, described mixing isomery N-phenyl-
The mol ratio of the double phthalimide of N '-phenyl-bis ether and water is 1:7-1:12, preferably 1:9-1:10.
8. according to the preparation method according to any one of claim 1-7, it is characterised in that in described step a), described pressure
Gauge pressure is 0.5-0.7MPa, preferably 0.6-0.65MPa；Heating-up temperature is 155-170 DEG C, preferably 160-165 DEG C；Hydrolysis time is
5-8 hour, preferably 6-7 hour.
9. according to the preparation method according to any one of claim 1-8, it is characterised in that the mineral acid added in step b) is
Hydrochloric acid, the hydroxide ion in the alkaline aqueous solution that in described mineral acid, free hydrionic integral molar quantity and step a) add
The ratio of mole is 1.5:1-2:1, preferably 1.7:1-1.8:1.
10. according to the preparation method according to any one of claim 1-9, it is characterised in that step c) is dehydrated and de-organic
The boiling temperature that temperature is weak water-soluble solvent of acid, the time is 5-12 hour, preferably 7-9 hour.
11. preparation methoies according to claim 1, it is characterised in that in described step c) filtrate cooling temperature be-10 to
80℃；
Preferably, first cool the filtrate to 70-80 DEG C and leach containing 3,3 ', 4,4 '-bis ether tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-bis-
Ether tetracarboxylic acid dianhydride and 2,3 ', 3, the solid of three kinds of isomers of 4 '-bis ether tetracarboxylic acid dianhydride, wherein, and 2,3 ', 3,4 '-bis ether four
Formic acid dianhydride content is in 11-15wt%, gross weights based on three kinds of isomer solid powder；Cool the filtrate to-10 to 0 DEG C again
Lower filtration, obtains 2,3 ', 3, and 4 '-bis ether tetracarboxylic acid dianhydride content is the bis ether tetramethyl of three kinds of isomer mixing of 75-87wt%
Acid dianhydride solid, the gross weight of the bis ether tetracarboxylic acid dianhydride of the three kinds of isomer mixing obtained after filtering based on residual filtrate；
Or, directly filtrate is down to-10 to 0 DEG C, leaches dianhydride solid, the raw material mixing isomery obtaining with adding in step a)
The mixing isomery bis ether tetracarboxylic acid dianhydride that in the double phthalimide of N-phenyl-N '-phenyl-bis ether, three kinds of isomer proportions are identical.
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| WO2020160115A1 (en) * | 2019-01-31 | 2020-08-06 | Sabic Global Technologies B.V. | Method of making a biphenol dianhydride composition, method for purification of a biphenol dianhydride, and poly(etherimide)s derived from the biphenol dianhydride |
| CN113667121A (en) * | 2021-09-15 | 2021-11-19 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyetherimide copolymer and preparation method thereof |
| US11623908B2 (en) | 2019-01-31 | 2023-04-11 | Shpp Global Technologies B.V. | Method for purification of a biphenol tetraacid composition and a biphenol tetraacid composition |
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| US11623908B2 (en) | 2019-01-31 | 2023-04-11 | Shpp Global Technologies B.V. | Method for purification of a biphenol tetraacid composition and a biphenol tetraacid composition |
| CN113667121A (en) * | 2021-09-15 | 2021-11-19 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyetherimide copolymer and preparation method thereof |
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