CN108164452B - A kind of preparation method of bis- (chlorophthalimides) - Google Patents
A kind of preparation method of bis- (chlorophthalimides) Download PDFInfo
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- CN108164452B CN108164452B CN201810133141.9A CN201810133141A CN108164452B CN 108164452 B CN108164452 B CN 108164452B CN 201810133141 A CN201810133141 A CN 201810133141A CN 108164452 B CN108164452 B CN 108164452B
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- C07—ORGANIC CHEMISTRY
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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Abstract
The present invention relates to the preparation methods of a kind of bis- (chlorophthalimides), phthalic anhydride is dissolved in water, it is passed through chlorine, reaction system is heated to 25 ~ 80 DEG C, it sustained response 8 ~ 12 hours, obtains meeting the monochloro phthalic anhydride for being used to prepare bis- (chlorophthalimide) techniques requirements；In the presence of the solvent by monochloro phthalic anhydride obtained and diamine compounds, it at 40 ~ 300 DEG C, is evacuated to -0.02 ~ -0.08MPa and reacts 8 ~ 16 hours, after reaction, through filter cake is obtained by filtration, filter cake is washed in boiling water, bis- (chlorophthalimides) are obtained by filtration.The method that the present invention produces the precursor bis- (chlorophthalimides) of polyimides is simple and convenient, is reacted under tiny structure, highly-safe, using only solvent, without using catalyst and dehydrating agent, and post-process simple, it is suitble to industrialized production, production cost is low, good product quality.
Description
Technical field
The present invention relates to the preparation methods of a kind of bis- (chlorophthalimides).
Background technique
Polyimides, polyetherimide are the most excellent model engineering plastics of performance in current industrialization, are had both
High temperature resistant and low temperature resistant dual heat resistance, while there is good heat insulating again, toughness is strong, and intensity is high, and it is resistant to chemical etching, it is close
The features such as low is spent, very extensive application is made it have, is such as applied to Kapton, polyimide foam insulation, medical treatment
Industry etc. has irreplaceable superiority especially in national defence new material and 3D printing technique.And bis- (chloro neighbour benzene two
Carboximide) it is being applied to prepare in polyimides or polyetherimide, there is huge technical advantage, it can direct one-step synthesis
Polyimides or polyetherimide, it is easy to operate, it is low in cost, it is advantageous to industrialized production.
The country prepares polyimides at present, polyetherimide main path is still to be produced using dianhydride and diamines polycondensation, should
Though the polyimides of various structures, polyetherimide can be made in method, production procedure is complicated, and required condition is harsh, reacts
Journey is not easy to control, and industrial production cost is higher, at home, preparation of industrialization bis- (chlorophthalimides) and uses it
Prepare polyimides, polyetherimide is rarely reported, the method is at home still in blank stage at present.In foreign patent and report
In road, the companies such as GE will prepare bis- (chlorophthalimides) industrialization, and for producing polyimides, polyethers acyl
Imines, but its method still has raw material complicated, needs that catalyst is added in reaction system, needs to add dehydrating agent, product in reaction process
The disadvantages of isolating and purifying difficulty.It is specific as follows:
A kind of diamine monomer, its synthetic method and polyimides prepared therefrom are described in 102491911 A of CN,
Its synthetic method is that nucleophilic displacement of fluorine occurs for 2- fluoro-4-nitrophenol and 4- nitro-chlorobenzene, prepares FNNB, FNNB is made of Pd/C
Catalyst, hydrazine hydrate make reducing agent and prepare diamine monomer, and diamine monomer and 6FDA occur polycondensation reaction, prepare polyimides.
This method introduces ether and fluorine-containing hydrophobic grouping in polyimides, prepares the weaker polyimides of polarity, can be used for wet sensitive
The research and development of original part.But this method raw material is not easy to obtain, and is unfavorable for industrialized production.
A kind of preparation method of double bromine phthalimides is described in CN102924361 A, this method is by adjacent benzene
Dicarboxylic acid anhydride and catalyst are put into oleum, and bromide is added dropwise, and produce tetrabromophthalic anhydride, tetrabromophthalic anhydride and diamines are dissolved in
In organic solvent, the double bromine phthalimides of product are obtained through high temperature dehydration after heating reaction.This method is preparing double bromines neighbours
When benzoylimino, complex process need to use the hazardous chemicals such as oleum, and pilot process is not easy to control, is not suitable for industry
Metaplasia produces.
The preparation method of a kind of aromatic dianhydride and polyimides is described in 105324384 A of CN, this method is virtue
Fragrant race's dianhydride reacts in organic solvent with diamines, generates the polyimides with microcellular structure, improves the processing of polyimides
Performance.But this method prepares dianhydride using multi-step, and expensive raw material price, complex process is cumbersome, is unfavorable for industrialized production.
A kind of method preparing bis- (halophthalimides) is described in 101128426 A of CN, in this method
In, dispersed using at least one halophthalic acid acid anhydride and at least one diamines in a solvent, in the work of amidation catalyst
Under, 150 DEG C or more are heated to, is maintained at 15% solid content, isolated bis- (bis (haloimides)s after fully reacting
Amine).This method only carries out single step reaction, is made bis- (halophthalimides), can be directly used for synthesizing poly- (ether) acyl Asia
Amine.Although the method process is fairly simple, there is still a need for amidated catalyst to exist for the method, and in product separating-purifying
It is relatively difficult.
A kind of method preparing bis- (phthalimides) is described in 106232678 A of CN, this method is to melt
Diphenyl sulphone (DPS), in sulfolane equal solvent, substituted phthalic anhydride is reacted with organic diamine, bis- (neighbours are directly made
Phthalimide).This method is although not required to plus catalyst, but the method is extremely stringent to water content requirement in reaction system,
During the reaction, it is desirable that hydrone content is necessarily less than 100ppm, this requirement all pole to industrialized producing technology and equipment
For harshness.
All there is certain lack when preparing bis- (chlorophthalimides) or poly- (ether) acid imide in above method
Therefore point is highly desirable to develop that a kind of reaction process is simple, is easy to control, low in cost and good product quality, be conducive to work
The preparation method of bis- (chlorophthalimides) that industry metaplasia produces.
Summary of the invention
The present invention overcomes complex process and separation when manufacturing bis- (chlorophthalimides) in the prior art
It the problem of purification difficult, provides that a kind of step is simple, and easy to operate, process safety is low in cost, is suitble to the double of industrialized production
The preparation method of (chlorophthalimide).
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
It is an object of the present invention to provide the preparation methods of a kind of bis- (chlorophthalimides), by chloro neighbour's benzene
Dicarboxylic acid anhydride and diamine compounds in the presence of the solvent, at 40~300 DEG C, it is anti-to be evacuated to -0.02~-0.08MPa
It answers, after reaction, through filter cake is obtained by filtration, the filter cake is washed in boiling water, bis- (chloro O-phthalics are obtained by filtration
Acid imide)；
The structural formula of the monochloro phthalic anhydride are as follows:
The structural formula of the diamine compounds are as follows:
H2N——R——NH2；
The general structure of bis- (chlorophthalimides) are as follows:
Wherein R be alkyl,
In the present invention, the monochloro phthalic anhydride is 3- monochloro phthalic anhydride, 4- chlorophthalic acid
The mixture of acid anhydride or 3- monochloro phthalic anhydride and 4- monochloro phthalic anhydride.
In the present invention, alkyl is the functional group containing only two kinds of carbon, hydrogen atoms, and two hydrogen originals are specially minused in alkane molecule
Alkyl made of son, preferably ethyl, propyl, butyl etc..
Preferably, the diamine compounds be ethylenediamine, it is propane diamine, butanediamine, 4,4`- diaminodiphenyl ether, right
Phenylenediamine, 4,4' diaminodiphenyl sulfone or 2,2'- bis- (trifluoromethyl) benzidine.
Preferably, the molar ratio of the monochloro phthalic anhydride and the diamine compounds be 1.5~
4:1.Further preferably 2~3:1, more preferably 2.1~2.6:1.
In the present invention, the solvent be at 20~80 DEG C be liquid, boiling point is 150~350 DEG C, be not involved in described
The solvent of the condensation reaction of monochloro phthalic anhydride and the diamine compounds.
Preferably, the solvent is silicone oil, glycerol, carbonic acid glyceride, long chain alkane, paraffin, ethylene carbonate, two
One or more of phenylate, polystream.
Preferably, the gross mass of the monochloro phthalic anhydride and the diamine compounds and the solvent
Feed intake mass ratio be 1:2~10.Further preferably 1:3~6.
Preferably, after reaction, it is recycled after the filtrate recycling when filter cake is obtained by filtration.
In the present invention, it is recycled after filtrate recycling and refers to that filtrate can be added directly into generation in reaction system of the invention
For partial solvent.
Preferably, the filtering is carried out using suction filtration.
Preferably, the reaction temperature is 100~200 DEG C.
Preferably, the specific embodiment of the preparation method are as follows: by the monochloro phthalic anhydride and described
Diamine compounds be added in the solvent, be stirred, heat the temperature of the reaction system to 40~300
DEG C, vacuumizing and keep the pressure of reaction system is -0.02~-0.08MPa, is reacted 8~16 hours, will be anti-after fully reacting
It answers object to filter to obtain the filter cake, the filter cake is added to the water, is heated to boiling, agitator treating, then through filtering
To bis- (chlorophthalimides).
It is further preferred that the monochloro phthalic anhydride the preparation method comprises the following steps: phthalic anhydride and water are added
Enter in reactor, chlorine is stirred and be passed through at 25~80 DEG C, insulation reaction 8~12 hours, is then filtered, washed, is dehydrated
The monochloro phthalic anhydride is made.
Most preferably, the specific embodiment of the preparation method are as follows: be dissolved in water phthalic anhydride, lead to
Enter chlorine, heat reaction system to 25~80 DEG C, sustained response 8~12 hours, obtains satisfaction and be used to prepare bis- (chloro neighbour benzene two
Carboximide) technique require monochloro phthalic anhydride；By the monochloro phthalic anhydride prepared according to the above method and described
Diamine compounds be added in the solvent, be stirred, heat the temperature of the reaction system to 40~300
DEG C, vacuumizing and keep the pressure of reaction system is -0.02~-0.08MPa, is reacted 8~16 hours, will be anti-after fully reacting
It answers object to filter to obtain the filter cake, the filter cake is added to the water, is heated to boiling, agitator treating, then through filtering
To bis- (chlorophthalimides).
Reaction equation of the invention are as follows:
Reaction of the invention is not necessarily to catalyst, and without dehydrating agent, solvent of the invention can take on catalyst, solvent simultaneously
And dehydrating agent, in addition, during the reaction, keeping system negative pressure state, pressure control guarantees in -0.02~-0.08MPa
The water that reaction generates can be automatic continuous evaporated from reaction system under micro-vacuum state, does not end up at reaction system
In.
Filter cake of the invention is crude product, and through filter cake in boiling water when agitator treating, surface impurity can be rinsed out directly, is produced
Composition granule expands in boiling water, and internal impurity is dissolved in water, and so as to the product purified, and purification process is simple.
Due to the implementation of above technical scheme, the invention has the following advantages over the prior art:
The method that the present invention produces imido precursor bis- (chlorophthalimides) is simple and convenient, under tiny structure
It is reacted, it is highly-safe, solvent is used only, without using catalyst and dehydrating agent, and post-processes simple, suitable industry metaplasia
It produces, production cost is low, good product quality.
Specific embodiment
The present invention will be further described in detail combined with specific embodiments below, but the present invention is not limited to following implementations
Example.Implementation condition used in the examples can do further adjustment according to specifically used different requirements, the implementation being not specified
Condition is the normal condition in the industry.It is obtained by those of ordinary skill in the art without making creative efforts
All other embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
310.8g (2.1mol) phthalic anhydride and 2488g water are added in reaction flask step (1), stir in 70 DEG C
It is uniformly dispersed, is slowly introducing 149.1g (2.1mol) chlorine into system under constant temperature stirring, sustained response 12 hours.Then, will
Temperature is down to room temperature suction filtration, and filter cake is washed with 300g clear water, then puts into vacuum dehydration 12 hours in reaction flask, pours out slowly cold
But, the monochloro phthalic anhydride solid for meeting technique requirement is obtained.
Step (2): will be according to 383.4g (2.1mol) monochloro phthalic anhydride and 60g made from step (1) method
(1mol) ethylenediamine is put into 1500g silicone oil, and stirring makes its evenly dispersed mixing, is heated reaction system to 150 DEG C, is evacuated to negative
Pressure is -0.05MPa, is persistently stirred to react 16 hours, is filtered after high performance liquid chromatography detection fully reacting, and filtrate is returned
It receives and is recycled, filter cake is bis- (phthalimide) crude product 398.4g, and crude product is put into boiling by crude yield 97.8%
Agitator treating in water, after boiling, impurity is removed inside product surface and particle, after suction filtration, obtains bis- (chlorine of the structure containing ethylene
For phthalimide) product 376.4g, product yield 92.4%；Through high performance liquid chromatography detection, purity is up to 99.4%.
Embodiment 2
Step (1): 310.8g (2.1mol) phthalic anhydride and 2488g water are added in reaction flask, are stirred in 70 DEG C
It is uniformly dispersed, is slowly introducing 149.1g (2.1mol) chlorine into system under constant temperature stirring, sustained response 12 hours.Then, will
Temperature is down to room temperature suction filtration, and filter cake is washed with 300g clear water, then puts into vacuum dehydration 12 hours in reaction flask, pours out slowly cold
But, the monochloro phthalic anhydride solid for meeting technique requirement is obtained.
Step (2): by monochloro phthalic anhydride 346.9g (1.9mol) made from step (1) and 86.4g (0.8mol)
P-phenylenediamine is put into 1800g atoleine, and stirring makes its evenly dispersed mixing, is heated reaction system to 170 DEG C, is evacuated to negative
Pressure is -0.08MPa, is filtered after being persistently stirred to react 10 hours, filtrate is recycled, and filter cake is bis- (adjacent benzene two
Carboximide) crude product 389.5g, crude product put into agitator treating in boiling water, after boiling, product by crude yield 96.3%
Impurity removes inside surface and particle, after suction filtration, obtains bis- (chlorophthalimide) products of aromatic structure
372.5g, product yield 92.1%, through high performance liquid chromatography detection, purity is up to 99.6%.
Embodiment 3
Step (1): 310.8g (2.1mol) phthalic anhydride and 2488g water are added in reaction flask, are stirred in 70 DEG C
It is uniformly dispersed, is slowly introducing 149.1g (2.1mol) chlorine into system under constant temperature stirring, sustained response 12 hours.Then, will
Temperature is down to room temperature suction filtration, and filter cake is washed with 300g clear water, then puts into vacuum dehydration 12 hours in reaction flask, pours out slowly cold
But, the monochloro phthalic anhydride solid for meeting technique requirement is obtained.
Step (2): by 273.8g (1.5mol) monochloro phthalic anhydride made from step (1) and 224g (0.7mol) 2,
2'- bis- (trifluoromethyl) benzidine is put into 2000g carbonic acid glyceride, and stirring makes its evenly dispersed mixing, and heating is anti-
Answer system to 180 DEG C, being evacuated to negative pressure is -0.07MPa, is filtered after being persistently stirred to react 14 hours, and filtrate is recycled and is recycled
It uses, filter cake is bis- (substituted phthalimide) crude product 456.1g, and crude product is put into boiling by crude yield 96.5%
Agitator treating in water, after boiling, impurity is removed inside product surface and particle, after suction filtration, obtains biphenyl type containing fluorine structure
Bis- (chlorophthalimide) product 433.8g, product yield 91.8%；Through high performance liquid chromatography detection, purity reaches
99.7%.
Embodiment 4
Step (1): 310.8g (2.1mol) phthalic anhydride and 2488g water are added in reaction flask, are stirred in 70 DEG C
It is uniformly dispersed, is slowly introducing 149.1g (2.1mol) chlorine into system under constant temperature stirring, sustained response 12 hours.Then, will
Temperature is down to room temperature suction filtration, and filter cake is washed with 300g clear water, then puts into vacuum dehydration 12 hours in reaction flask, pours out slowly cold
But, the monochloro phthalic anhydride solid for meeting technique requirement is obtained.
Step (2): by 237.3g (1.3mol) monochloro phthalic anhydride made from step (1) and 100g (0.5mol) 4,
4`- diaminodiphenyl ether is put into 2000g ethylene carbonate, and stirring makes its evenly dispersed mixing, and heating reaction system is extremely
190 DEG C, being evacuated to negative pressure is -0.05MPa, is filtered after being persistently stirred to react 10 hours, filtrate is recycled, filter cake
For bis- (substituted phthalimide) crude product 308.8g, crude product is put into boiling water and is stirred by crude yield 96.7%
Washing, after boiling, impurity is removed inside product surface and particle, after suction filtration, obtains bis- (chloro neighbours of the aromatic series containing ether structure
Phthalimide) product 291.8g, product yield 91.4%；Through high performance liquid chromatography detection, purity is up to 99.5%.
Embodiment 5
Step (1): 310.8g (2.1mol) phthalic anhydride and 2488g water are added in reaction flask, are stirred in 70 DEG C
It is uniformly dispersed, is slowly introducing 149.1g (2.1mol) chlorine into system under constant temperature stirring, sustained response 12 hours.Then, will
Temperature is down to room temperature suction filtration, and filter cake is washed with 300g clear water, then puts into vacuum dehydration 12 hours in reaction flask, pours out slowly cold
But, the monochloro phthalic anhydride solid for meeting technique requirement is obtained.
Step (2): by 365.1g (2.0mol) monochloro phthalic anhydride made from step (1) and 198.6g (0.8mol)
4,4'- diaminodiphenylsulfones are put into 3000g polystream, and stirring makes its evenly dispersed mixing, heating reaction system to 180
DEG C, being evacuated to negative pressure is -0.04MPa, is filtered after being persistently stirred to react 12 hours, filtrate is recycled, filter cake is
Crude product is put into stirring in boiling water and washed by bis- (substituted phthalimide) crude product 513.0g, crude yield 95.9%
It washs, after boiling, impurity is removed inside product surface and particle, after suction filtration, obtains bis- (chloro neighbour's benzene of aromatic series structure containing sulfone
Dicarboximide) product 489.4g, product yield 91.5%；Through high performance liquid chromatography detection, purity is up to 99.7%.
Comparative example 1
Will according to embodiment 1 step (1) the method prepare monochloro phthalic anhydride 237.3g (1.3mol) with
59.4g (0.5mol) m-phenylene diamine (MPD) is put into 1300g glycerol, and stirring makes its evenly dispersed mixing, heating reaction system to 150
DEG C, negative pressure device is not enabled, is filtered, filtrate is recycled, filter cake after being persistently stirred to react 15 hours under normal pressure
For bis- (chlorophthalimide) crude product 196.2g, crude yield is only 70.4%, and crude product is put into boiling water and is stirred
Washing, after boiling, impurity is removed inside product surface and particle, after suction filtration, obtains bis- (chloro neighbours of aromatic series structure containing sulfone
Phthalimide) product 154.1g, product yield is only 55.3%；Through high performance liquid chromatography detection, purity 99.2%.
Comparative example 2
Will according to embodiment 1 step (1) the method prepare 219.1g (1.2mol) monochloro phthalic anhydride with
99.1g (0.5mol) diaminodiphenylmethane is put into 1900g diphenyl ether, and stirring makes its evenly dispersed mixing, heating reaction
System does not enable negative pressure device, is filtered after being persistently stirred to react 16 hours under normal pressure to 170 DEG C, and filtrate is recycled and is recycled
It uses, filter cake is bis- (chlorophthalimide) crude product 190.3g, and crude yield is only 63.4%, and crude product is put into often
Agitator treating in warm water after suction filtration, obtains bis- (chlorophthalimide) products of aromatic series structure containing sulfone without boiling
171.7g, product yield are only 57.2%；Through high performance liquid chromatography detection, purity 92.7%.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes according to the present invention
The equivalent change or modification of work, should be covered by the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of bis- (chlorophthalimide) class compounds, it is characterised in that: by chloro O-phthalic
Acid anhydrides and diamine compounds in the presence of the solvent, at 40 ~ 300 DEG C, are evacuated to -0.02 ~ -0.08MPa reaction, reaction
After, through filter cake is obtained by filtration, the filter cake is washed in boiling water, bis- (chlorophthalimides) are obtained by filtration
Class compound；
The structural formula of the monochloro phthalic anhydride are as follows:
,
The structural formula of the diamine compounds are as follows:
,
The general structure of bis- (chlorophthalimide) class compounds are as follows:
；
Wherein, R be ethyl, propyl, butyl,、、Or；
The solvent is one of silicone oil, glycerol, carbonic acid glyceride, paraffin, ethylene carbonate, diphenyl ether, polystream
Or it is several.
2. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
The molar ratio of the monochloro phthalic anhydride and the diamine compounds is 1.5 ~ 4:1, and the chloro is adjacent
The mass ratio that feeds intake of the gross mass of phthalate anhydride and the diamine compounds and the solvent is 1:2 ~ 10.
3. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
The solvent be liquid, boiling point at 20 ~ 80 DEG C be 150 ~ 350 DEG C, be not involved in the monochloro phthalic anhydride with
The solvent of the condensation reaction of the diamine compounds.
4. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
After reaction, it is recycled after the filtrate recycling when filter cake is obtained by filtration.
5. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
The filtering is carried out using filtering.
6. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
The reaction temperature is 100 ~ 200 DEG C.
7. the preparation method of bis- (chlorophthalimide) class compounds according to claim 1, it is characterised in that:
The specific embodiment of the preparation method are as follows: add the monochloro phthalic anhydride and the diamine compounds
Enter into the solvent, be stirred, heats the temperature of the reaction system to 40 ~ 300 DEG C, vacuumize and keep reacting
The pressure of system is -0.02 ~ -0.08MPa, is reacted 8 ~ 16 hours, after fully reacting, reactant is filtered to obtain the filter
The filter cake is added to the water by cake, is heated to boiling, agitator treating, then obtains bis- (chloro neighbour benzene two through filtering
Carboximide) class compound.
8. the preparation method of bis- (chlorophthalimide) class compounds according to any one of claim 1 to 7,
It is characterized by: the monochloro phthalic anhydride the preparation method comprises the following steps: phthalic anhydride and water are added in reactor,
Chlorine is stirred and be passed through at 25 ~ 80 DEG C, insulation reaction 8 ~ 12 hours, is then filtered, washed, is dehydrated the chloro for being made described
Phthalic anhydride.
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| PCT/CN2019/074225 WO2019154279A1 (en) | 2018-02-09 | 2019-01-31 | Method for preparing bis(chlorophthalimide) |
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| CN114195697B (en) * | 2021-12-21 | 2023-07-04 | 四川大学 | Dichloro diphthalimide intermediate and synthetic method and application thereof |
| CN114014794A (en) * | 2021-12-21 | 2022-02-08 | 四川大学 | Method for refining products in production of dichloro-bis-phthalimide intermediate |
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Non-Patent Citations (1)
| Title |
|---|
| Poly(thioether imide)s via chloro-displacement polymerization;L.J.Mathias er al.;《Polymer Bulletin》;19950331;第34卷(第3期);287-94 |
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