CN106279085B - A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride - Google Patents
A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods for mixing isomery bis ether tetracarboxylic acid dianhydride, include the following steps：A) it is pressurizeing under heating condition, the double phthalimide solids of mixing isomery N phenyl N ' phenyl bis ether hydrolyze in alkaline aqueous solution, generate water-oil phase mixed liquor；After detaching oil phase, paste solidliquid mixture is obtained after dehydration cooling；B) inorganic acid is added in into the paste solidliquid mixture that step a) is obtained, obtains sticky mixing isomery bis ether tetracarboxylic acid colloidal solution；Organic acid is added in into colloidal solution, the sticky suspended matter in colloidal solution is made to be separated into powdered suspended matter；C) weak water-soluble solvent is added in into the powdered suspended matter that step b) is obtained, system is heated, the organic acid added in removing water and step b) completely, the salt in heat filtering removing system are obtained after filtrate cooling containing the solid precipitate for mixing isomery bis ether tetracarboxylic acid dianhydride.
Description
Technical field
The present invention relates to bis ether tetracarboxylic acid dianhydride synthetic technologys, and in particular to the synthesis of mixing 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 for synthesizing special material polyimides.Use bis ether tetracarboxylic acid two
Polyimide material prepared by acid anhydride has the characteristics that high tenacity, high intensity, can be used at 230 DEG C for a long time.
A kind of synthetic method of bis ether tetracarboxylic acid dianhydride is described in US publication US5068353；China discloses special
Also the preparation method of preparation 3,3 ', 4,4 '-bisphenol-A bis ether tetracarboxylic acid dianhydride is individually described in sharp CN104529966A.It is above-mentioned
The method introduced in publication approximately as：
The double phthalimides of N- phenyl-N '-phenyl-bis ether are acidified again after ordinary-pressure hydrolysis, obtain pair not soluble in water
Ether tetracarboxylic acid solid；
Bis ether tetracarboxylic acid solid is obtained into bis ether tetracarboxylic acid dianhydride after thermal dehydration；
Its synthetic route reaction equation is as follows：
Wherein, R represents aromatic hydrocarbyl, such as Deng；X represents K, Na etc.
There are three types of isomers for bis ether tetracarboxylic acid dianhydride, are 3,3 ', 4 respectively, 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 difference 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
According to materials synthesis theory, if these three isomers are used in mixed way, as the raw material for preparing polyimides, that
Prepared polyimides can have higher glass transition temperature, but with relatively low glutinous stream temperature, this allows for isomery
Polyimides has the characteristics that more resistant to high temperature and easily machine-shaping, therefore, the mixing isomery bis ether that three kinds of isomers coexist
The study on the synthesis of tetracarboxylic acid dianhydride becomes the research hotspot of polyimides academia.
However it is found that many problems in isomery bis ether tetracarboxylic acid dianhydride building-up process is mixed：
One mixes isomers there are three types of the double phthalimides of isomery N- phenyl-N '-phenyl-bis ether, in basic hydrolysis only
There is a kind of isomers can be with complete hydrolysis, and other two isomers is unable to complete hydrolysis in a short time, needs heating at least 200
Hour or more could hydrolyze completely；
Second, mixing isomery bis ether tetracarboxylic acid aqueous solution of alkali metal salt, after steaming water, acidification, what is obtained is that one kind dissolves in
The colloidal solution of the mixing isomery bis ether tetracarboxylic acid of water, therefore bis ether tetracarboxylic acid solid can not be obtained.
Third, bis ether tetracarboxylic acid solid in air, in a vacuum thermal dehydration formed dianhydride during, dehydration it is slower
And nigrescence apt to deteriorate；Dehydrating effect is preferable in acetic anhydride, but can have certain corrosion, and acetic acid to equipment during dry solvent
Acid anhydride belongs to control chemicals, and unnecessary trouble can be brought in course of industrialization.
There is the presence of one, 2 two difficult point, lead to the progress of synthesis of mixing isomery bis ether tetracarboxylic acid dianhydride almost
It stays cool, up to the present there is not yet 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride or contain 2,3 ', 3,4 '-bis ether tetramethyl
The report that the product of acid dianhydride mixing isomery bis ether tetracarboxylic acid dianhydride is synthesized.
Therefore, it is necessary to develop a kind of new synthetic method, successfully prepare containing 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride
Mix the product of isomery bis ether tetracarboxylic acid dianhydride.
Invention content
For mixing isomery bis ether tetracarboxylic acid dianhydride problem in synthesis, the purpose of the present invention is intended to provide one kind
The preparation method of isomery bis ether tetracarboxylic acid dianhydride is mixed, after the double phthalimide hydrolysis of mixing isomery N- phenyl-N '-phenyl-bis ether
Organic acid is introduced as dispersant, and effectively dehydration is realized by the addition of weak water-soluble solvent, it is different so as to successfully prepare mixing
Structure bis ether tetracarboxylic acid dianhydride solid.
In order to realize more than goal of the invention, technical scheme is as follows：
A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride, includes the following steps：
A) it is pressurizeing under heating condition, the double phthalimide solids of mixing isomery N- phenyl-N '-phenyl-bis ether are in alkalinity
It is hydrolyzed in aqueous solution, generates the water-oil phase mixed liquor of bis ether tetramethyl acid salt aqueous solution and aniline；After detaching oil phase, heated aqueous
The water of partial volume is steamed, paste solidliquid mixture is obtained after cooling；
B) inorganic acid is added in into the paste solidliquid mixture that step a) is obtained, obtains sticky mixing isomery bis ether tetramethyl
Acid colloids solution；Organic acid is added in into colloidal solution, the sticky suspended matter in colloidal solution is made to be separated into powdered suspended matter；
C) weak water-soluble solvent is added in into the powdered suspended matter that step b) is obtained, 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 ', 3,4 ' after filtrate cooling-it is different
The solid precipitate of the mixing isomery bis ether tetracarboxylic acid dianhydride of structure body.
The invention also includes step d), the filter cake that the solid powder precipitate that step c) is obtained is obtained by filtration carries out vacuum
Dry, dried solid after crushed, obtains mixing isomery bis ether tetracarboxylic acid dianhydride product.
In the present invention, in step a), the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether are carbon atom number
34 to the 43 double phthalimides of mixing isomery bis ether, including but not limited to：N- phenyl-N '-phenyl-triphen containing three kinds of isomers
Double phthalimides of the double phthalimide of diether, N- phenyl-N '-phenyl containing three kinds of isomers-bisphenol-A diether or containing three kinds of isomers
Double phthalimides of N- phenyl-N '-phenyl-'-biphenyl diphenol diether etc..
In the present invention, three kinds of isomers of the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether are respectively
3,3 ', 4,4 '-N- phenyl-N '-phenyl-bis ether double phthalimide, 2,3 ', the double phthaloyls of 3,4 '-N- phenyl-N '-phenyl-bis ether are sub-
Amine and 2, the double phthalimides 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 preferable 50-55wt%, based on mixing isomery N-
The total weight of the double phthalimides of phenyl-N '-phenyl-bis ether, other two kinds of isomers can be combined with arbitrary proportion.
In step a) of the present invention, the 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, mixing isomery N- phenyl-N '-phenyl-bis ether pair phthalimide and alkaline aqueous solution
In alkali molar ratio be 1:4 to 1:6, preferably 1:5-1:5.5.
In step a) of the present invention, the pressure (gauge pressure) is 0.5-0.7MPa, preferably 0.6-0.65MPa；It is described to add
The temperature of heat is 155-170 DEG C, preferably 160-165 DEG C.Hydrolysis time is 5-8 hours, preferably 6-7 hours.
In step a) of the present invention, the double phthalimide solids of mixing isomery N- phenyl-N '-phenyl-bis ether are in alkaline water
When beginning is hydrolyzed in solution, the molar ratio of the double phthalimides of the N- phenyl-N '-phenyl-bis ether and water is 1:7-1:12, preferably
1:9-1:10。
After step a) separation oil phase of the present invention, heated aqueous steams the water of 50-70% volumes, based on water phase totality
Product, paste solidliquid mixture is obtained after being then cooled to room temperature.
In the step b), add in inorganic acid and be acidified, the inorganic acid is the hydrochloric acid that mass concentration is 30-37%.
In the present invention, the alkalinity that hydrionic integral molar quantity is added in step a) of dissociating in the inorganic acid added in step b)
The ratio between mole of hydroxide ion in aqueous solution is 1.5:1-2:1, preferably 1.7:1-1.8:1.
In the present invention, organic acid is added in into colloidal solution under agitation in step b), peptizaiton can be played,
The organic acid is formic acid and/or acetic acid, and addition is the double phthaleins of mixing isomery N- phenyl-N ' described in step a)-phenyl-bis ether
The 5-15wt% of acid imide quality, preferably 6-10wt%.
In the present invention, in the step c), weak 20 DEG C of solubility in water of water-soluble solvent wants 0.05-2.4g/
100g；Between boiling point is 130-181 DEG C, preferably between 152-173 DEG C.Preferably, it is molten to include ketone for the weak water-soluble solvent
It is one or more in agent；It is highly preferred that the weak water-soluble solvent includes but not limited to cyclohexanone, methyln-hexyl ketone, cycloheptanone, 3-
It is one or more in octanone and cyclopentanone etc..
System is heated under stiring after adding in weak water-soluble solvent in step c) of the present invention, carries out dehydration, reaction
Temperature is the boiling temperature of weak water-soluble solvent, the organic acid added in the water and step b) in removing system, dehydration
Time is 5-12 hours, preferably 7-9 hours.Mixing isomery N- benzene of the additive amount of weak water-soluble solvent for addition in step a)
8-12 times, preferably 9-10 times of the double phthalimide quality of base-N '-phenyl bis ether.
Since water and weak water-soluble solvent dissolubility are bad, in solvent refluxing, water and solvent azeotropic are condensed
Afterwards, water and solvent are layered in water knockout drum, and since water is bigger than the density of the weak water-soluble solvent in the present invention, water is under
Layer.Meanwhile mixing isomery bis ether tetracarboxylic acid can be dehydrated into anhydride reactant, therefore in solvent refluxing in a solvent, mix
The water that isomery bis ether tetracarboxylic acid is taken off also while discharges system.
After removing the organic acid added in water and step b) in the present invention, in step c) completely, heat filtering is carried out, maintains heat
The temperature of filtering 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 in step c), after filtrate cooling, according to cooling
Different temperature afterwards obtains the mixing isomery bis ether tetramethyl of different composition ratio in filter cake that can respectively after filtration and filtrate
Acid dianhydride.
As a preferred solution, 70-80 DEG C is first cooled the filtrate to, is filtered, filter out containing 3,3 ', 4,4 '-
Bis ether tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-bis ether tetracarboxylic acid dianhydride and 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride, three kinds of isomers
Solid powder, wherein 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride content is in 11-15wt%, based on three kinds of isomer solid powder
Total weight；Residual filtrate is cooled at -10 to 0 DEG C again and is filtered, obtains 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride content is in 75-
The bis ether tetracarboxylic acid dianhydride solid of three kinds of isomers mixing of 87wt%, the three kinds of isomers obtained after being filtered based on residual filtrate
The total weight of the bis ether tetracarboxylic acid dianhydride of mixing.
Alternatively, filtrate directly is down to -10 to 0 DEG C as another preferred scheme, dianhydride solid is filtered out, obtains and walks
Three kinds of isomer proportions are identical in rapid a) the middle double phthalimides of the raw material mixing isomery N- phenyl-N '-phenyl-bis ether added in mixes
Close isomery bis ether tetracarboxylic acid dianhydride.
In the present invention, the solid powder precipitate containing mixing isomery bis ether tetracarboxylic acid dianhydride obtained in step c) passes through
Vacuum drying, the vacuum drying temperature is 110-170 DEG C, preferably 140 to 150 DEG C.The vacuum degree is -0.098MPa
To -0.1MPa.The two steps drying time is 5-12 hours, preferably 7-9 hours.
The method of the present invention can realize that feed stock conversion reaches 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 are as follows：
1st, it solves mixing isomery bis ether tetracarboxylic acid to be dissolved in water and mixing isomery bis ether tetracarboxylic acid dianhydride solid can not be obtained
The problem of；
2nd, by controlling the difference of filtration temperature, the bis ether tetracarboxylic acid dianhydride of different isomer composition can be obtained.
Description of the drawings
Fig. 1 is mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride through aniline treated HPLC spectrograms
Fig. 2 is the HPLC spectrograms for mixing isomery '-biphenyl diphenol diether tetracarboxylic acid colloidal solution
Specific embodiment
Embodiment 1
Mix the synthesis of isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride
565.2g water, 62.8g mixing isomery N- phenyl-N '-phenyl-biphenyl two are added in the compressive reaction kettle of 1000ML
The double phthalimides of phenol diether (are 1 with water quality ratio:9, wherein 2,2 ', 3,3 '-bis- phthalimides, 2,3 ', 3,4 '-bis- phthaloyls are sub-
Amine and 3,3 ', the ratios of 4,4 '-bis- phthalimides are that the mass ratio of three is 1:2:2), the sodium hydroxide (20g) of 0.5mol, will
Reactor seals, and opens stirring, is 0.6MPa by temperature up to reactor pressure (gauge pressure, similarly hereinafter), at this time reactor temperature
It is about 160 DEG C, after reacting 7 hours, stops heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, upper strata is gone to separatory funnel point
Oily aniline.Remaining liquid is added in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating,
The water of about 60% volume is steamed, into paste after cooling.
The hydrochloric acid 103ml (being equivalent to pure hydrogen chloride 0.85mol) of a concentration of 30wt% is added in into obtained liquid/paste,
The sticky colloidal solution of celadon is formed in there-necked flask.The acetic acid of 3.14g is added in into bottle, solid precipitation occurs in bottle.
670g cyclohexanone (2.4g/100g, 152 DEG C of boiling point during 20 DEG C of solubility in water) is added in into reaction bulb, is stirred
Mix lower heating.When temperature rises to about 152 DEG C during i.e. cyclohexanone boiling point, the acid steamed is gradually carried over reaction system.When point
When occurring in hydrophone without droplet, illustrate that reaction terminates, three kinds of '-biphenyl diphenol diether tetracarboxylic acids are dehydrated into acid anhydride and finish.Reaction is about
Need 7 hours.
Solidliquid mixture is filtered while hot.Filtrate is cooled to 0 DEG C.The solid of precipitation is continued to filter, filter cake-
0.098MPa, it is dried 7 hours at 145 DEG C, solid is crushed, obtain mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride.
Above-mentioned three kinds of content of isomer analytic processes of mixing isomery '-biphenyl diphenol diether tetracarboxylic acid dianhydride being prepared are such as
Under：0.03g samples is taken to add in 20ml chromatographically pure grade N-Methyl pyrrolidones, after being dissolved under low-grade fever stirring, add in accurate weighing
High-purity aniline of two times of moles of dianhydride sample, stirring after ten minutes, turn the reaction completely of '-biphenyl diphenol diether tetracarboxylic acid dianhydride
The double phthalimides of N- phenyl-N '-phenyl-'-biphenyl diphenol diether of corresponding isomers are turned to, then by solution chromatographically pure grade first
Base pyrrolidones is diluted to 100ml, and liquid-phase chromatographic analysis, mobile phase are carried out after shaking up：Acetonitrile/water=67/33 (volume ratio)；Stream
Fast 1.0ml/min；UV detectors, wavelength 254nm；C18 chromatographic columns, chromatogram are shown in Fig. 1.
The content difference of corresponding '-biphenyl diphenol diether tetracarboxylic acid dianhydride isomers is analyzed and is scaled according to chromatographic results
For：2,2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4,4 '-isomers mass ratio are 1:2:2；Three kinds different
Structure body purity summation is 99.0%, yield 92%.
Embodiment 2
Mix the synthesis of isomery triphen diether tetracarboxylic acid dianhydride
552g water, 55.2g mixing isomery N- phenyl-N '-phenyl-'-biphenyl diphenol are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of diether:10, wherein 2,2 ', 3,3 '-bis- phthalimides, 2,3 ', 3,4 '-bis- phthaloyls are sub-
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
Stirring is opened in sealing, is 0.7MPa by temperature up to reactor pressure, and reactor temperature is about 167 DEG C at this time, and reaction 8 is small
Shi Hou stops heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, the oily aniline on upper strata is removed with separatory funnel point.It will be remaining
Liquid add in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating steams about 70% volume
Water, after steaming water, into paste after cooling.
A concentration of 37% hydrochloric acid 101ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
1.2mol), the sticky colloidal solution of celadon is formed in there-necked flask.The acetic acid of 8.28g is added in into bottle, solid analysis occurs in bottle
Go out.
662.4g2- octanones (0.09g/100g, 173 DEG C of boiling point during 20 DEG C of solubility in water) are added in into reaction bulb,
Stirring is lower to heat.When temperature rises to about 173 DEG C of i.e. methyln-hexyl ketone boiling points, the acid steamed is gradually carried over reaction system.When point
When occurring in hydrophone without droplet, illustrate that reaction terminates, three kinds of triphen diether tetracarboxylic acids are dehydrated into acid anhydride and finish.Reaction takes around
5 hours.It is down to room temperature.
Solidliquid mixture is filtered while hot.Filtrate is cooled to -10 DEG C.The solid of precipitation is continued to filter, filter cake-
0.099MPa, it is dried 12 hours at 140 DEG C, solid is crushed, obtain mixing isomery triphen diether tetracarboxylic acid dianhydride.Through dividing
Analysis, 2,2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4,4 '-isomers mass ratio is 1:2:1, three kinds different
Structure body purity summation is 99.0%, yield 91.5%.
Embodiment 3
Mix the synthesis of isomery bisphenol-A diether tetracarboxylic acid dianhydride
469g water, 67g (common 0.1mol) mixing isomery N- phenyl-N '-phenyl-are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of bisphenol-A diether:7, 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,
Reactor is sealed, opens stirring, is 0.5MPa by temperature up to reactor pressure, reactor temperature is about 155 DEG C at this time,
After reaction 5 hours, stop heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, the oily benzene on upper strata is removed with separatory funnel point
Amine.Remaining liquid is added in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating steams about
The water of 60% volume steams about residue 240ml thick liquids after water, into paste after cooling.
A concentration of 30% hydrochloric acid 67ml or so (being equivalent to pure hydrogen chloride 0.6mol) is added in into obtained liquid/paste,
The sticky colloidal solution of celadon is formed in there-necked flask.The formic acid of 4.02g is added in into bottle, solid precipitation occurs in bottle.
The cycloheptanone (0.15g/100g, boiling point 181 during 20 DEG C of solubility in water) of 603g is added in into reaction bulb, is stirred
Mix lower heating.When temperature rises to about 181 DEG C of i.e. cycloheptanone boiling points, the acid steamed is gradually carried over reaction system.When dividing water
When occurring in device without droplet, illustrate that reaction terminates, three kinds of bisphenol-A diether tetracarboxylic acids are dehydrated into acid anhydride and finish.Reaction takes around
12 hours.
Solidliquid mixture is filtered while hot.Filtrate is cooled to -5 DEG C, and the solid of precipitation is continued to filter, filter cake -
0.098MPa, it is dried 8 hours at 140 DEG C, solid is crushed, obtain mixing isomery triphen diether tetracarboxylic acid dianhydride.Through dividing
Analysis, 2,2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4,4 '-isomers mass ratio is 15:55:30, three kinds
Enantiomeric purity summation is 99.2%, yield 93%.
Embodiment 4
Mix the synthesis of isomery resorcinol diether tetracarboxylic acid dianhydride
662.4g water, 55.2g mixing isomery N- phenyl-N '-phenyl-isophthalic two are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of phenol diether:12, 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,
Reactor is sealed, opens stirring, is 0.65MPa by temperature up to reactor pressure, reactor temperature is about 165 at this time
DEG C, after reacting 6 hours, stop heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, the oily on upper strata is removed with separatory funnel point
Aniline.Remaining liquid is added in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating steams about
The water of 50% volume, into paste after cooling.
A concentration of 37% hydrochloric acid 83ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
0.99mol), the sticky colloidal solution of celadon is formed in there-necked flask.The acetic acid of 5.52g is added in into bottle, solid occurs in bottle
It is precipitated.
The 3- octanones (0.82 during 20 DEG C of solubility in water, boiling point 157) of 441.6g are added in into reaction bulb, under stirring
Heating.When temperature rises to about 157 DEG C of i.e. 3- octanones boiling points, the acid steamed is gradually carried over reaction system.When in water knockout drum
When no droplet occurs, illustrate that reaction terminates, three kinds of resorcinol diether tetracarboxylic acids are dehydrated into acid anhydride and finish.Reaction takes around 9
Hour.
Solidliquid mixture is filtered into desalination while hot.Filtrate is cooled to 80 DEG C, filters out a part of solid again, is denoted as solid
Body A；The filtrate for filtering out solid A continues to be cooled to 0 DEG C, filters again, and a part of solid of getting back is denoted as solid B.At 170 DEG C
Under, close under the conditions of absolute pressure, solid A and solid B are dried 9 hours respectively.
Through analysis：2 in solid A, 2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4, the ratio of 4 '-isomers
Example is respectively 8:8:48, three kinds of enantiomeric purity summations are 99.2%, 2,3 ', 3, and 3 '-content of isomer is 12.5%, and yield is
53%.
2 in solid B, 2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4, the ratio difference of 4 '-isomers
It is 2:27:7,2,3 ', 3,3 '-content of isomer is 75%, and three kinds of enantiomeric purity summations are 99.0%, yield 40.2%.
It is 93.2% to mix isomery resorcinol diether tetracarboxylic acid dianhydride total recovery.
Embodiment 5
Mix the synthesis of isomery bisphenol S diether tetracarboxylic acid dianhydride
657.4g water, 69.2g mixing isomery N- phenyl-N '-phenyl-bisphenol S are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of diether:12, wherein 2,2 ', 3,3 '-bis- phthalimides, 2,3 ', 3,4 '-bis- phthaloyls are sub-
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,
Reactor is sealed, opens stirring, is 0.63MPa by temperature up to reactor pressure, reactor temperature is about 163 at this time
DEG C, after reacting 6.5 hours, stop heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, the oil on upper strata is removed with separatory funnel point
Shape aniline.Remaining liquid is added in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating steams
The water of about 60% volume, into paste after cooling.
A concentration of 37% hydrochloric acid 90ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
0.91mol), the sticky colloidal solution of celadon is formed in there-necked flask.The formic acid of 5.536g is added in into bottle, solid occurs in bottle
It is precipitated.
The cyclopentanone (20 DEG C of solubility 0.05 in water, 130 DEG C of boiling point) of 657.4g is added in into reaction bulb, under stirring
Heating.When temperature rises to about 130 DEG C of i.e. cyclopentanone boiling points, the acid steamed is gradually carried over reaction system.When in water knockout drum
When no droplet occurs, illustrate that reaction terminates, three kinds of bisphenol S diether tetracarboxylic acids are dehydrated into acid anhydride and finish, and it is small that reaction takes around 8
When.
Solidliquid mixture is filtered into desalination while hot.Filtrate is cooled to 80 DEG C,
A part of solid is filtered out again, is denoted as solid C；The filtrate for filtering out solid C continues to be cooled to 0 DEG C, filters again, again
A part of solid is obtained, is denoted as solid D.It is respectively that solid C and solid D dryings 5 is small at 110 DEG C, under the conditions of -0.098MPa
When.
Through analysis：2 in solid C, 2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4, the ratio of 4 '-isomers
Example is respectively 8:5:32,2,3 ', 3,4 '-content of isomer is 11%, and three kinds of enantiomeric purity summations are 99.2wt%, and yield is
45%.
2 in solid D, 2 ', 3,3 '-isomers, 2,3 ', 3,4 '-isomers and 3,3 ', 4, the ratio difference of 4 '-isomers
It is 2:48:5,2,3 ', 3,4 '-isomers is 87%, and three kinds of enantiomeric purity summations are 99.0%, yield 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 are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of diether:10, wherein 2,2 ', 3,3 '-bis- phthalimides, 2,3 ', 3,4 '-bis- phthaloyls are sub-
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 reactor temperature is about 167 DEG C at this time, reacts 8 hours
Afterwards, stop heat drop to room temperature.Reaction kettle is opened, reaction solution is taken out, the oily aniline on upper strata is removed with separatory funnel point.It will be remaining
Liquid is added in the 2000ml three-necked flasks equipped with water knockout drum and ball condenser, normal heating, steams the water of about 70% volume,
After steaming water, into paste after cooling.
A concentration of 37% hydrochloric acid 101ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
1.2mol), the sticky colloidal solution of celadon is formed in there-necked flask.After colloidal solution sampling liquid-phase chromatographic analysis, analysis
As a result it is Fig. 2, has obtained three peaks, three components are respectively 2,2 ', 3,3 '-triphen diether tetracarboxylic acid, 2, and 3 ', 3,4 '-triphen
Diether tetracarboxylic acid and 3,3 ', 4, colloidal solution is filtered, can not obtain solid product by 4 '-triphen diether tetracarboxylic acid.
Colloidal solution analytic process is as follows：0.3g solution examples is taken to be diluted with water to 100ml, shake up rear sample introduction.Liquid phase color
Spectral condition is as follows：Mobile phase：Acetonitrile/1wt% ammonium dihydrogen phosphate aqueous solution=30/70 (volume ratio)；Flow velocity 1.0ml/min；UV
Detector, wavelength 254nm；C18 chromatographic columns.
Comparative example 2
657.4g water, 69.2gN- phenyl-N '-phenyl -3,3 ', 4,4 '-bis-phenol are added in the compressive reaction kettle of 1000ML
(mass ratio with water is 1 to the double phthalimides of S diether:12), the potassium hydroxide (29.12g) of 0.52mol, reactor is sealed, is opened
Stirring is opened, by up to 100 DEG C of temperature, is at this time normal pressure in reaction kettle, after reacting 24 hours, stops heat drop to room temperature.Open reaction
Kettle takes out reaction solution, and the oily aniline on upper strata is removed with separatory funnel point.Remaining liquid is added in equipped with water knockout drum and spherical shape
In the 2000ml three-necked flasks of condenser, normal heating steams the water of about 60% volume, into paste after cooling.
A concentration of 37% hydrochloric acid 90ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
0.91mol), white solid precipitation is formed in there-necked flask.After precipitation is stirred evenly, 100 DEG C are heated to, keeps the temperature 5 hours.
After heat preservation, system is down to room temperature, solid is filtered, and carried out filter cake after washing 5 times with pure water, will filtered
Cake is put into convection oven to be 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 is added in 500ml acetic anhydrides, after being heated to reflux 2 hours, drop
Temperature filters solid, and filter cake in 100 DEG C, -0.098MPa is dried in vacuo 2 hours, obtains containing only isomery in product after testing
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 kettle of 1000ML, 2 ', 3,3 '-bis-phenol
(mass ratio with water is 1 to the double phthalimides of S diether:12), the potassium hydroxide (29.12g) of 0.52mol, reactor is sealed, is opened
Stirring is opened, by up to 160 DEG C of temperature, is at this time 0.6MPa in reaction kettle, after reacting 8 hours, stops heat drop to room temperature.Open reaction
Kettle takes out reaction solution, and the oily aniline on upper strata is removed with separatory funnel point.Remaining liquid is added in equipped with water knockout drum and spherical shape
In the 2000ml three-necked flasks of condenser, normal heating steams the water of about 60% volume, into paste after cooling.
A concentration of 37% hydrochloric acid 90ml or so is added in into obtained liquid/paste and (is equivalent to pure hydrogen chloride
0.91mol), white solid precipitation is formed in there-necked flask.After precipitation is stirred evenly, 100 DEG C are heated to, keeps the temperature 5 hours.
After heat preservation, system is down to room temperature, solid is filtered, and carried out filter cake after washing 5 times with pure water, will filtered
Cake is put into convection oven to be 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 is added in 500ml acetic anhydrides, after being heated to reflux 5 hours, drop
Temperature filters solid, and filter cake in 100 DEG C, -0.098MPa is dried in vacuo 2 hours, product is obtained and contains only 2,2 ', 3 after testing,
3 '-bisphenol S diether tetracarboxylic acid dianhydride.Yield 89.3%, purity 98.7%.
Comparative example 4
Reference《Takekoshi T.J.Polym.Sci, 1967,11:609》Method carries out synthesis of polyimides resin.
Gathered respectively using the mixing isomery diether tetracarboxylic acid dianhydride prepared in embodiment 1 to 3 with 4,4 '-diaminodiphenyl ether
It closes, obtains polyimide resin 1-3.
For the solid A and solid B obtained using embodiment 4 respectively with 4, the polymerization of 4 '-diaminodiphenyl ether obtains polyimides
Resin 4-1 and resin 4-2.
For the solid C and solid D obtained using embodiment 5 respectively with 4, the polymerization of 4 '-diaminodiphenyl ether obtains polyimides
Resin 5-1 and resin 5-2.
The 2,2 ', 3 of the preparation of 3,3 ', 4,4 '-bisphenol S diether tetracarboxylic acid dianhydride and comparative example 3 prepared using comparative example 2,
For 3 '-bisphenol S diether tetracarboxylic acid dianhydride product respectively with 4,6 He of polyimide resin is prepared in the polymerization of 4 '-diaminodiphenyl ether
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 1 polyimide resin 1-7 of table
Above example, which can be seen that the present invention, can prepare 3 kinds of isomers (especially 2,3 ', 3,4 '-isomers) together
When existing mixing diether tetracarboxylic acid dianhydride solid, and the polyamides that the mixing diether tetracarboxylic acid dianhydride that the present invention is used to prepare synthesizes
Imide resin has the molecular weight of higher glass transition temperature, lower glutinous stream temperature and bigger.
The performance of resin 5-1 and resin 5-2 and resin 6 and resin 7 carries out comparison as can be seen that due to preparing resin 5-1
With in the raw materials bisphenol S diether tetracarboxylic acid dianhydrides of resin 5-2 containing dissymmetrical structure 2,3 ', 3,4 '-isomers, with 4,
The obtained performance of resin is superior to resin 6 and resin 7 after the polymerization of 4 '-diaminodiphenyl ether, illustrate containing 2,3 ', 3,4 '-no
The polyimides of symmetrical structure has the advantage of apparent thermal property and processing performance than the polyimides of symmetrical structure.Together
When, the performance of resin 5-1 is good but better than the performance of resin 6 and resin 7 not as good as the performance of 5-2, this illustrates 2 in polyimides,
3 ', 3,4 '-dissymmetrical structure unit is more, and the performance of resin is better, more advantageous in terms of heat resistance and processability.
Claims (23)
1. a kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride, includes the following steps：
A) it is pressurizeing under heating condition, the double phthalimide solids of mixing isomery N- phenyl-N '-phenyl-bis ether are water-soluble in alkalinity
It is hydrolyzed in liquid, generates the water-oil phase mixed liquor of bis ether tetramethyl acid salt aqueous solution and aniline；After detaching oil phase, heated aqueous steams
The water of partial volume obtains paste solidliquid mixture after cooling；
B) inorganic acid is added in into the paste solidliquid mixture that step a) is obtained, obtains sticky mixing isomery bis ether tetracarboxylic acid glue
Liquid solution；Organic acid is added in into colloidal solution, the sticky suspended matter in colloidal solution is made to be separated into powdered suspended matter；
C) weak water-soluble solvent is added in into the powdered suspended matter that step b) is obtained, system is heated, remove water and step completely
It is rapid b) in the organic acid that adds in, the salt in heat filtering removing system obtained containing 2,3 ', 3,4 '-isomers after filtrate cooling
Mixing isomery bis ether tetracarboxylic acid dianhydride solid precipitate.
2. preparation method according to claim 1, which is characterized in that the organic acid added in step b) into colloidal solution
For formic acid and/or acetic acid, addition is the double phthalimide quality of mixing isomery N- phenyl-N ' described in step a)-phenyl-bis ether
5-15wt%.
3. preparation method according to claim 2, which is characterized in that organic acid addition is different for mixing described in step a)
The 6-10wt% of the double phthalimide quality of structure N- phenyl-N '-phenyl-bis ether.
4. preparation method according to claim 1, which is characterized in that weak 20 DEG C of water-soluble solvent is in water described in step c)
In solubility be 0.05-2.4g/100g；Between boiling point is 130-181 DEG C；The weak water-soluble solvent is included in ketones solvent
It is one or more.
5. preparation method according to claim 4, which is characterized in that the weak water-soluble solvent boiling point is 152-173 DEG C
Between；The weak water-soluble solvent includes one or more in cyclohexanone, methyln-hexyl ketone, cycloheptanone, 3- octanones and cyclopentanone.
6. according to the preparation method described in claim 1 or 4 or 5, which is characterized in that the additive amount of the weak water-soluble solvent is
8-12 times of the double phthalimide quality of the mixing isomery N- phenyl-N ' added in step a)-phenyl bis ether.
7. preparation method according to claim 6, which is characterized in that the additive amount of the weak water-soluble solvent is step a)
9-10 times of the double phthalimide quality of the mixing isomery N- phenyl-N ' of middle addition-phenyl bis ether.
8. preparation method according to claim 1, which is characterized in that in the step a), the mixing isomery N- phenyl-
Mixing isomery bis ether double phthalimides of the double phthalimides of N '-phenyl-bis ether for carbon atom number 34 to 43；The mixing isomery N-
The content of the double phthalimides of 2,3 ', 3,4 '-N- phenyl-N '-phenyl-bis ether is in the double phthalimides of phenyl-N '-phenyl-bis ether
20-55wt%, the total weight based on the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether.
9. preparation method according to claim 8, which is characterized in that the mixing isomery N- phenyl-N '-phenyl-bis ether
Double phthalimides are selected from the double phthalimides of N- phenyl-N '-phenyl containing three kinds of isomers-triphen diether, containing three kinds of isomers
The double phthalimides of N- phenyl-N '-phenyl-bisphenol-A diether or N- phenyl-N '-phenyl-'-biphenyl diphenol diether containing three kinds of isomers
Double phthalimides；2,3 ', 3,4 '-N- phenyl-N '-benzene in the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether
The content of the double phthalimides of base-bis ether is 35-55wt%, based on the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether
Total weight.
10. preparation method according to claim 9, which is characterized in that the mixing isomery N- phenyl-N '-phenyl-bis ether
The content of the double phthalimides of 2,3 ', 3,4 '-N- phenyl-N '-phenyl-bis ether is 50-55wt% in double phthalimides, based on mixing
The total weight of the double phthalimides of isomery N- phenyl-N '-phenyl-bis ether.
11. preparation method according to claim 1, which is characterized in that in the step a), the alkaline aqueous solution includes
Sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution；The double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether with
The molar ratio of alkali in alkaline aqueous solution is 1:4 to 1:6.
12. preparation method according to claim 11, which is characterized in that the alkaline aqueous solution is water-soluble for sodium hydroxide
Liquid；The molar ratio of the double phthalimides of mixing isomery N- phenyl-N '-phenyl-bis ether and the alkali in alkaline aqueous solution is 1:5 to
1:5.5。
13. preparation method according to claim 1, which is characterized in that in the step a), mixing isomery N- phenyl-N '-
When the double phthalimide solids of phenyl-bis ether hydrolyze beginning in alkaline aqueous solution, mixing isomery N- phenyl-the N '-phenyl-is bis-
The molar ratio of the double phthalimides of ether and water is 1:7-1:12.
14. preparation method according to claim 13, which is characterized in that mixing isomery N- phenyl-the N '-phenyl-is bis-
The molar ratio of the double phthalimides of ether and water is 1:9-1:10.
15. preparation method according to claim 1, which is characterized in that in the step a), the pressure gauge pressure is 0.5-
0.7MPa；Heating temperature is 160-165 DEG C；Hydrolysis time is 6-7 hours.
16. preparation method according to claim 15, which is characterized in that the pressure gauge pressure is 0.6-0.65MPa；Heating
Temperature is 160-165 DEG C；Hydrolysis time is 6-7 hours.
17. preparation method according to claim 1, which is characterized in that the inorganic acid added in step b) is hydrochloric acid, described
The mole of the hydroxide ion to dissociate in inorganic acid in the alkaline aqueous solution that hydrionic integral molar quantity and step a) are added in it
Than being 1.5:1-2:1.
18. preparation method according to claim 17, which is characterized in that hydrionic total moles of dissociating in the inorganic acid
The ratio between mole of hydroxide ion in the alkaline aqueous solution that amount is added in step a) is 1.7:1-1.8:1.
19. preparation method according to claim 1, which is characterized in that be dehydrated in step c) and the temperature of de- organic acid is
The boiling temperature of weak water-soluble solvent, time are 5-12 hours.
20. preparation method according to claim 19, which is characterized in that the time of dehydration and de- organic acid is 7-9 hours.
21. preparation method according to claim 1, which is characterized in that in the step c) filtrate cooling temperature for -10 to
80℃。
22. preparation method according to claim 21, which is characterized in that filtrate first cools the filtrate in the step c)
70-80 DEG C filters out containing 3,3 ', 4,4 '-bis ether tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-bis ether tetracarboxylic acid dianhydride and 2,3 ', 3,4 '-
The solid of three kinds of isomers of bis ether tetracarboxylic acid dianhydride, wherein, 2,3 ', 3,4 '-bis ether tetracarboxylic acid dianhydride content in 11-15wt%,
Total weight based on three kinds of isomer solid powder；It cools the filtrate at -10 to 0 DEG C and filters again, obtain 2,3 ', 3,4 '-it is bis-
The bis ether tetracarboxylic acid dianhydride solid that three kinds of isomers that ether tetracarboxylic acid dianhydride content is 75-87wt% mix, based on residual filtrate
The total weight of the bis ether tetracarboxylic acid dianhydride of three kinds of isomers mixing obtained after filtering.
23. preparation method according to claim 21, which is characterized in that filtrate directly drops filtrate in the step c)
To -10 to 0 DEG C, dianhydride solid is filtered out, is obtained double with the raw material mixing isomery N- phenyl-N '-phenyl-bis ether added in step a)
The identical mixing isomery bis ether tetracarboxylic acid dianhydride of three kinds of isomer proportions in phthalimide.
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| JP2022519078A (en) | 2019-01-31 | 2022-03-18 | エスエイチピーピー グローバル テクノロジーズ べスローテン フェンノートシャップ | Methods for Purifying Biphenol Quartic Acid Compositions and Biphenol Quartic Acid Compositions |
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