CN113666940B - Preparation method of troger base-containing dianhydride - Google Patents
Preparation method of troger base-containing dianhydride Download PDFInfo
- Publication number
- CN113666940B CN113666940B CN202111006640.XA CN202111006640A CN113666940B CN 113666940 B CN113666940 B CN 113666940B CN 202111006640 A CN202111006640 A CN 202111006640A CN 113666940 B CN113666940 B CN 113666940B
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- acid
- hours
- troger base
- troger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of troger base contained dianhydride, which comprises the following steps: and (3) reacting the amino-containing aromatic acid anhydride compound with a formaldehyde initiator to obtain the troger base-containing dianhydride. The method synthesizes the troger base-containing dianhydride by a one-step method, shortens the reaction route, reduces the post-treatment steps and improves the yield. The purity of the troger base-containing dianhydride is more than or equal to 99.8%, and the yield is more than or equal to 86.5%.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of troger base-containing dianhydride.
Background
Polyimide is used as a very important functional material and has wide application in the aspects of aerospace, electronic circuits, separation membranes and the like. However, the disadvantages of the conventional polyimide, such as poor solubility, high melting resistance, and non-processability, limit its applications. Conventional polyimides also do not meet specific performance requirements for specific application scenarios. The dianhydride monomer is a basic raw material for preparing polyimide, and based on the designability of a molecular structure, the novel dianhydride is developed to improve the related performance of the polyimide by starting from the molecular structure design of the monomer, so that the dianhydride monomer has very important significance for optimizing the performance of the polyimide and widening the application of the polyimide.
One of the methods for improving the properties of polyimide is to introduce a rigid twisted structure into the main chain of the polyimide molecule, which can effectively induce the formation of self-microporous structure, thereby preparing self-microporous polyimide with excellent thermal, mechanical and processability properties. And towards the base of Gelsel: (
base, abbreviated as TB) as a typical group having a V-shaped rigid bicyclic twisted structure can effectively cut off the conjugation of electron clouds between polymer molecular chains and in the chains, thereby reducing the dielectric constant of polyimide. Furthermore, troger bases have electron-rich characteristics similar to those of nitrogen heterocyclic structures such as benzimidazole, and thus improve the adhesion properties between polyimide and metal. Thus, troger bases are ideal groups for improving the processability, separation, dielectric and adhesion of polymers. Recently, polymer materials containing troger baseThe material has been separated in the gas (e.g. CO) 2 Trapping, hydrogen separation, etc.), proton exchange membranes, optically transparent membranes, etc.
At present, methods for preparing diamine monomers containing troger bases, tetraphenol monomers and polymers thereof have been reported. For example, CN110606951A discloses a semi-aromatic polyimide material, a preparation method, a use thereof and a gas separation membrane comprising the same. The molecular chain of the semi-aromatic polyimide has a Rungel base structure, and the aromatic ring structure in the main chain is matched with the alicyclic structure, so that the prepared gas separation membrane has good mechanical property, heat resistance and stability, and has high permeability coefficient and good selectivity when being used for hydrogen separation and air separation. Therefore, the troger base group plays an important role in polyimide, and efficient production of a troger base-containing monomer is also a problem to be solved.
CN106749297A discloses a preparation method of troger base contained dianhydride. 4-aminophthalic acid (4-APA) and formaldehyde initiator are used as initial reactants to synthesize troger base dianhydride-6H, 12H-5, 11-methylene dibenzo [ b, f ] [1,5] diazacyclo-2, 3,8, 9-tetracarboxylic dianhydride (TB-DA) by a two-step method. However, the preparation method requires the production of TB-DA by a two-step reaction, which not only increases the reaction time and wastes the cost, but also decreases the yield.
Therefore, under the conditions of saving cost, shortening reaction route and improving yield, the development of a preparation method containing troger base dianhydride is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing troger base-containing dianhydride. Through the reaction of the amino-containing aromatic anhydride compound and the formaldehyde initiator, the synthesis of the anhydride containing the troger base by a one-step method is realized, the reaction process is shortened, the post-treatment steps are reduced, and the yield is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of troger base-containing dianhydride, which comprises the following steps: reacting an amino-containing aromatic anhydride compound having a structure represented by formula I with a formaldehyde-originating agent to obtain the troger base-containing dianhydride having a structure represented by formula II;
wherein, the ring Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted C10-C30 condensed ring aryl and Ar 1 -L-Ar 2 Any one of the above; ar (Ar) 1 、Ar 2 Each independently selected from any one of substituted or unsubstituted C6-C30 aryl; l is any one of single bond, -CO-, -O-or-SO-; ring Ar, ar 1 、Ar 2 Wherein said substituted substituents are each independently selected from the group consisting of halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 And an unsubstituted or halogenated C1-C10 straight-chain or branched-chain alkyl group.
According to the invention, the amino-containing aromatic acid anhydride compound and the formaldehyde initiator are used as initial reactants, a crude product containing the troger base dianhydride is synthesized by adopting a one-step method, and the high-purity troger base dianhydride is obtained through post-treatment steps such as reduced pressure distillation, drying, recrystallization and the like, and is not required to be separated through a chromatographic column, so that the reaction process is shortened, the post-treatment steps are reduced, and the yield is improved.
In the present invention, the C10 to C30 condensed ring aryl group includes C10, C12, C14, C16, C18, C20, C22, C24, C26, and C28 condensed ring aryl groups, and exemplarily includes but is not limited to: naphthyl, fluorenyl, anthryl, indenyl, phenanthryl, pyrenyl, acenaphthenyl, triphenylenyl, pyrenyl, phenanthrenyl, and phenanthrenyl,
Acenaphthenyl, perylenyl, and the like.
The C6 to C30 aryl group includes aryl groups of C6, C8, C9, C10, C12, C13, C14, C15, C16, C18, C20, C22, C24, C26, C28, etc., and exemplarily includes but is not limited to: phenyl, biphenyl, naphthyl,Fluorenyl, anthracenyl, indenyl, phenanthrenyl pyrenyl, acenaphthenyl a triphenylene group,
Acenaphthenyl, peryleneyl, and the like.
In the present invention, the halogen includes fluorine, chlorine, bromine or iodine; the following relates to the same description with the same meaning.
In the present invention, the "halo" means that at least one H in the group is substituted by a halogen (e.g., F, cl, br, or I).
The unsubstituted or halogenated C1 to C10 linear or branched alkyl group includes unsubstituted or halogenated C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 linear or branched alkyl groups, and exemplarily includes but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perchloroethyl and the like.
As a preferred embodiment of the present invention, the ring Ar is selected from any one of the following groups:
wherein denotes the fused site of the group.
R 1 、R 2 Each independently selected from halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 Any of unsubstituted or halogenated C1 to C10 linear or branched alkyl groups, which may be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 linear or branched alkyl groups, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perchloroethyl and the like.
m 1 Is an integer of 0 to 3, and may be, for example0、1、2、3。
m 2 Is an integer of 0 to 5, and may be, for example, 0, 1, 2,3, 4 or 5.
m 3 Is an integer of 0 to 6, and may be, for example, 0, 1, 2,3, 4, 5 or 6.
m 4 Is an integer of 0 to 4, and may be, for example, 0, 1, 2,3 or 4.
Preferably, the amino aromatic anhydride-containing compound has any one of the following structures:
wherein R is 1 ～R 10 Each independently selected from-H, halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 Any of unsubstituted or halogenated C1 to C10 linear or branched alkyl groups, which may be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 linear or branched alkyl groups, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perchloroethyl and the like.
Preferably, the formaldehyde source comprises any one of formaldehyde, paraformaldehyde, hexamethylenetetramine, dimethoxymethane or ethylene glycol dimethyl ether or a combination of at least two of them.
Preferably, the amount of the substance of the formaldehyde initiator is 2 to 10mol, for example, 2mol, 3mol, 4mol, 5mol, 6mol, 7mol, 8mol, 9mol, 10mol, or the like based on 1mol of the substance of the amino-containing aromatic acid anhydride compound.
Preferably, the reaction is carried out in a solvent.
Preferably, the solvent is an acidic solvent.
Preferably, the acidic solvent has a pH of 0.5 to 6, for example, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, and the like.
Preferably, the acidic solvent comprises any one of trifluoroacetic acid, polyphosphoric acid, formic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, or hydrochloric acid, or a combination of at least two thereof.
Preferably, the polyphosphoric acid is phosphorus pentoxide (P) 2 O 5 ) The content of (b) is more than 82% by mass, and may be, for example, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90% or the like.
Preferably, the amino-containing aromatic anhydride compound is mixed with a formaldehyde initiator, and then a solvent is added for reaction.
Preferably, the mixing temperature is-5 ~ 30 ℃, for example can be-5 ℃, 0 ℃,5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ etc..
In the invention, the mixing temperature of the amino-containing aromatic anhydride compound and the formaldehyde initiator is not excessively high, when the mixing temperature is higher than 30 ℃, the reactants are easy to deteriorate and the reaction activity is reduced, and the molecular weight of the obtained product is low.
Preferably, the reaction temperature is-15 ~ 180 ℃, for example can be-15 ℃, 0 ℃, 15 ℃, 30 ℃, 45 ℃,60 ℃, 75 ℃, 90 ℃, 100 ℃,120 ℃, 150 ℃, 180 ℃ etc..
Preferably, the reaction time is 24 to 240 hours, and for example, the reaction time may be 24 hours, 48 hours, 72 hours, 96 hours, 120 hours, 150 hours, 180 hours, 210 hours, 240 hours, and the like.
In the invention, the reaction time is related to the reaction temperature and the molecular weight of reactants, and when the reaction temperature is high, the reaction time is long; the molecular weight of the reactant is large, and the reaction time is long.
Preferably, the solvent is added dropwise.
Preferably, the dropping time is 1 to 180min, for example, 1min, 2min, 4min, 8min, 16min, 32min, 64min, 128min, 150min, 180min, etc.
Preferably, the reaction further comprises a post-treatment step.
Preferably, the work-up comprises distillation, filtration, drying and recrystallization.
Preferably, the distillation method is vacuum distillation.
Preferably, the drying temperature is 60-180 ℃, for example, can be 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃,120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃.
Preferably, the drying time is 2 to 72 hours, and for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours and the like can be used.
Preferably, the reagent for recrystallization is acetic anhydride.
Preferably, the reagent is used in an amount of 1.1 to 100mol, for example, 1.1mol, 10mol, 20mol, 30mol, 40mol, 50mol, 60mol, 70mol, 80mol, 90mol, 100mol, etc., based on 1mol of the substance of the crude product to be recrystallized.
Preferably, the specific method of recrystallization comprises: and mixing the crude product with a recrystallization reagent, refluxing, cooling, standing for crystallization, filtering and drying to obtain the troger base-containing dianhydride.
The refluxing time is preferably 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 4 hours, 8 hours, 10 hours, 12 hours, 16 hours, 20 hours, 24 hours, or the like.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing an amino-containing aromatic acid anhydride compound with a formaldehyde initiator at the temperature of-5 to 30 ℃, dropwise adding an acidic solvent, reacting for 24 to 240 hours at the temperature of-15 to 180 ℃, and carrying out reduced pressure distillation and drying to obtain a crude product containing troger base dianhydride;
(2) And (2) mixing the crude product obtained in the step (1) with acetic anhydride, refluxing, cooling, standing and crystallizing to obtain the troger base-containing dianhydride.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the troger base-containing dianhydride provided by the invention takes the amino-containing aromatic anhydride compound and the formaldehyde initiator as initial reactants, and synthesizes the troger base-containing dianhydride by a 'one-step method', so that the reaction process is shortened, the post-treatment steps are reduced, and the yield is improved; the yield of the troger base-containing dianhydride is more than or equal to 86.5 percent, and the purity of the troger base-containing dianhydride is more than or equal to 99.8 percent.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of troger base-containing dianhydride, which comprises the following specific steps:
mixing 50mmol of amino-containing aromatic anhydride compound A and 120mmol of paraformaldehyde (avadin, analytically pure) at-5 ℃, stirring, dripping 140mL of acetic acid into a reaction bottle for 30min, and reacting at-15 ℃ for 80h; after the reaction is finished, distilling under reduced pressure, filtering, and drying at 80 ℃ for 24 hours to obtain a crude product containing troger base dianhydride;
mixing the crude product containing troger base dianhydride and acetic anhydride in a mass ratio of 1:25, refluxing for 5 hours, cooling, standing for crystallization, filtering and drying to obtain the troger base contained dianhydride A1, wherein the reaction route is shown as follows:
example 2
The embodiment provides a preparation method of troger base-containing dianhydride, which comprises the following specific steps:
mixing and stirring 60mmol of amino-containing aromatic anhydride compound B and 120mmol of ethylene glycol dimethyl ether at 30 ℃, dripping 120mL of trifluoroacetic acid into a reaction bottle for 60min, and reacting at 60 ℃ for 240h; after the reaction is finished, carrying out reduced pressure distillation, filtering and drying at 60 ℃ for 24 hours to obtain a crude product containing troger base dianhydride;
mixing the crude product containing troger base dianhydride and acetic anhydride according to the mass ratio of 1:25, refluxing for 5 hours, cooling, standing for crystallization, filtering and drying to obtain the troger base contained dianhydride B1, wherein the reaction route is shown as follows:
example 3
The embodiment provides a preparation method of troger base-containing dianhydride, which comprises the following specific steps:
mixing 40mmol amino aromatic anhydride compound C and 120mmol dimethoxymethane at 15 deg.C, stirring, and adding dropwise 140mL polyphosphoric acid (avastin, purity not less than 99.0%, P) into the reaction flask 2 O 5 Content of 85%), the dripping time is 30min, and the reaction is carried out for 80h at 180 ℃; after the reaction is finished, carrying out reduced pressure distillation, filtering and drying at 120 ℃ for 12h to obtain a crude product containing troger base dianhydride;
mixing the crude product containing troger base dianhydride and acetic anhydride according to the mass ratio of 1:25, mixing, refluxing for 5 hours, cooling, standing for crystallization, filtering and drying to obtain the troger base contained dianhydride C1, wherein the reaction route is shown as follows:
example 4
The embodiment provides a preparation method of troger base-containing dianhydride, which comprises the following specific steps:
mixing and stirring 40mmol of amino-containing aromatic anhydride compound C and 360mmol of dimethoxymethane at 10 ℃, dripping 500mL of trifluoroacetic acid into a reaction bottle for 150min, and reacting at 25 ℃ for 200h; after the reaction is finished, carrying out reduced pressure distillation and filtration, and drying at 120 ℃ for 36 hours to obtain a crude product containing troger base dianhydride;
mixing the crude product containing troger base dianhydride and acetic anhydride in a mass ratio of 1:90 mixing, refluxing for 10h, cooling, standing for crystallization, filtering and drying to obtain the troger base contained dianhydride D1, wherein the reaction route is shown as follows:
example 5
The embodiment provides a preparation method of troger base-containing dianhydride, which comprises the following specific steps:
mixing and stirring 40mmol of amino-containing aromatic anhydride compound E and 200mmol of dimethoxymethane at 30 ℃, dripping 300mL of trifluoromethanesulfonic acid into a reaction bottle for 100min, and reacting at 120 ℃ for 24h; after the reaction is finished, carrying out reduced pressure distillation, filtering and drying at 120 ℃ for 24 hours to obtain a crude product containing troger base dianhydride;
mixing the crude product containing troger base dianhydride and acetic anhydride in a mass ratio of 1:1.5 mixing, refluxing for 2h, cooling, standing for crystallization, filtering and drying to obtain troger base contained dianhydride E1, wherein the reaction route is shown as follows:
comparative example 1
The comparative example provides a preparation method of troger base-containing dianhydride, which is different from the embodiment in that the troger base-containing dianhydride is synthesized by a two-step method by taking aminophthalic acid as a starting reactant. The method comprises the following specific steps:
(1) Mixing 60mmol of aminophthalic acid (4-APA) and 120mmol of paraformaldehyde at-10 ℃, stirring, dropwise adding 120mL of trifluoroacetic acid into a reaction bottle for 60min, and reacting at 0 ℃ for 100h; after the reaction is finished, reduced pressure distillation is carried out, the residual liquid is poured into a beaker filled with ice blocks, extracted by dichloromethane, washed by water and anhydrous Na 2 SO 4 Drying, column chromatography separation, petroleum ether: ethyl acetate =5:1, brown solid TB-ACID was obtained in 86% yield.
(2) Weighing 5.2g of TB-ACID, adding the TB-ACID into a 100mL single-neck flask filled with 50mL of acetic anhydride, refluxing for 24h under the protection of nitrogen atmosphere, performing suction filtration after the temperature of the system is reduced to room temperature, washing a filter cake with acetone, and drying for 24h in a vacuum oven at 80 ℃ to obtain a crude product containing the troger base dianhydride.
Recrystallizing the crude product containing troger base dianhydride in acetic anhydride to obtain the troger base dianhydride, wherein the reaction route is shown as follows:
performance testing
(1) Purity: testing by high performance liquid chromatography with a model 2695/2996/2465 of Waters;
(2) Yield = (final purified product mass/theoretical calculated product mass) × 100%.
Specific results are shown in table 1:
TABLE 1
As can be seen from the above table, the method for preparing the troger base-containing dianhydride provided by the invention uses the amino-containing aromatic anhydride compound and the formaldehyde initiator as initial reactants, and adopts a one-step method to synthesize the troger base-containing dianhydride, so that the purity is high and the yield is high.
As can be seen from examples 1 to 5, the purity of the prepared troger base-containing dianhydride is greater than or equal to 99.8%, and the yield is greater than or equal to 86.5%. While it can be seen by comparative example 1 that the yield of troger base containing dianhydride prepared by the two-step process is only 71.4%. The amino-containing aromatic anhydride compound is used as the starting material, so that the yield is improved, the reaction steps and the post-treatment steps are reduced, the cost is saved, and the product loss is avoided.
In conclusion, the preparation method for synthesizing the troger base-containing dianhydride by adopting the one-step method has the advantages of simple reaction route, high purity of the obtained product and high yield, and can be used as a monomer raw material for preparing the polyimide with micropores and the related functional polymer.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (26)
1. A preparation method of troger base contained dianhydride is characterized by comprising the following steps: reacting an amino-containing aromatic anhydride compound having a structure represented by formula I with a formaldehyde-originating agent to obtain the troger base-containing dianhydride having a structure represented by formula II;
wherein, the ring Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted C10-C30 condensed ring aryl and Ar 1 -L-Ar 2 Any one of the above;
Ar 1 、Ar 2 each independently selected from any one of substituted or unsubstituted C6-C30 aryl;
l is any one of single bond, -CO-, -O-or-SO-;
ring Ar, ar 1 、Ar 2 Wherein said substituted substituents are each independently selected from the group consisting of halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 Unsubstituted or halogenatedAny one of C1 to C10 straight chain or branched chain alkyl groups of (1).
2. The method according to claim 1, wherein the ring Ar is selected from any one of the following groups:
wherein represents the fused site of the group;
R 1 、R 2 each independently selected from halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 Any one of unsubstituted or halogenated C1-C10 straight chain or branched chain alkyl;
m 1 is an integer of 0 to 3;
m 2 is an integer of 0 to 5;
m 3 is an integer of 0 to 6;
m 4 is an integer of 0 to 4.
3. The method of claim 1 or 2, wherein the amino aromatic anhydride-containing compound has any one of the following structures:
wherein R is 1 ～R 10 Each independently selected from-H, halogen, -OH, -COOH, -SO 3 H、-NO 2 、-H 2 PO 4 And an unsubstituted or halogenated C1-C10 straight-chain or branched alkyl group.
4. The method according to claim 1, wherein the formaldehyde source agent comprises any one of formaldehyde, paraformaldehyde, hexamethylenetetramine, dimethoxymethane or ethylene glycol dimethyl ether or a combination of at least two of them.
5. The production method according to claim 1, wherein the amount of the substance of the formaldehyde initiator is 2 to 10mol based on 1mol of the substance of the amino-aromatic acid anhydride-containing compound.
6. The method according to claim 1, wherein the reaction is carried out in a solvent.
7. The method according to claim 1, wherein the solvent is an acidic solvent.
8. The method according to claim 7, wherein the acidic solvent has a pH of 0.5 to 6.
9. The method according to claim 7, wherein the acidic solvent comprises any one of trifluoroacetic acid, polyphosphoric acid, formic acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and hydrochloric acid, or a combination of at least two thereof.
10. The method according to claim 9, wherein the polyphosphoric acid has a phosphorus pentoxide content greater than 82% by mass.
11. The method according to claim 1, wherein the amino-aromatic acid anhydride-containing compound is mixed with the formaldehyde initiator, and then the mixture is reacted with the solvent.
12. The method of claim 11, wherein the mixing temperature is-5 to 30 ℃.
13. The method according to claim 11, wherein the reaction temperature is-15 to 180 ℃.
14. The method according to claim 11, wherein the reaction time is 24 to 240 hours.
15. The production method according to claim 11, wherein the solvent is added dropwise.
16. The method according to claim 15, wherein the dropping time is 1 to 180min.
17. The method of claim 1, further comprising a post-treatment step after the reaction.
18. The method of claim 17, wherein the post-treatment comprises distillation, filtration, drying and recrystallization.
19. The method of claim 18, wherein the distillation is carried out under reduced pressure.
20. The method of claim 18, wherein the drying temperature is 60 to 180 ℃.
21. The method of claim 18, wherein the drying time is 2 to 72 hours.
22. The method according to claim 18, wherein the recrystallization reagent is acetic anhydride;
23. the method of claim 22, wherein the reagent is used in an amount of 1.1 to 100mol based on 1mol of the substance of the crude product to be recrystallized.
24. The method according to claim 18, wherein the recrystallization comprises:
and mixing the crude product with a recrystallization reagent, refluxing, cooling, standing for crystallization, filtering and drying to obtain the troger base-containing dianhydride.
25. The method of claim 24, wherein the refluxing time is 1 to 24 hours.
26. The method of claim 1, comprising the steps of:
(1) Mixing an amino-containing aromatic acid anhydride compound with a formaldehyde initiator at the temperature of-5 to 30 ℃, dropwise adding an acidic solvent, reacting for 24 to 240 hours at the temperature of-15 to 180 ℃, and carrying out reduced pressure distillation and drying to obtain a crude product containing troger base dianhydride;
(2) And (2) mixing the crude product obtained in the step (1) with acetic anhydride, refluxing, cooling, standing and crystallizing to obtain the troger base-containing dianhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006640.XA CN113666940B (en) | 2021-08-30 | 2021-08-30 | Preparation method of troger base-containing dianhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006640.XA CN113666940B (en) | 2021-08-30 | 2021-08-30 | Preparation method of troger base-containing dianhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113666940A CN113666940A (en) | 2021-11-19 |
| CN113666940B true CN113666940B (en) | 2022-10-21 |
Family
ID=78547446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111006640.XA Active CN113666940B (en) | 2021-08-30 | 2021-08-30 | Preparation method of troger base-containing dianhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113666940B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749297A (en) * | 2016-11-24 | 2017-05-31 | 湖南文理学院 | A kind of preparation method of the dianhydride of base containing Chao Geer |
-
2021
- 2021-08-30 CN CN202111006640.XA patent/CN113666940B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749297A (en) * | 2016-11-24 | 2017-05-31 | 湖南文理学院 | A kind of preparation method of the dianhydride of base containing Chao Geer |
Non-Patent Citations (2)
| Title |
|---|
| 基于Troger"s Base的∧-型有机硼类光电功能材料的设计、合成与性能研究;习鹤;《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》;20130915;全文 * |
| 朝格尔碱衍生物的制备及其催化的4H-色烯并[2,3-b]吡啶-3-腈的合成;陈雯;《有机化学》;20201231;第40卷(第4期);988-996 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113666940A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112851611B (en) | Preparation method of 4, 4' -diphenyl ether tetracarboxylic dianhydride | |
| Feng et al. | All-carbocycle hydrocarbon thermosets with high thermal stability and robust mechanical strength for low-k interlayer dielectrics | |
| CN113666940B (en) | Preparation method of troger base-containing dianhydride | |
| US4801682A (en) | High temperature fluorinated polymer | |
| CN108164452B (en) | A kind of preparation method of bis- (chlorophthalimides) | |
| CN113277950A (en) | Asymmetric aromatic diamine monomer containing terphenyl large-substitution side group and polyimide | |
| CN114702433B (en) | Diamine monomer of low dielectric constant polyimide, synthesis method and application | |
| CN113717177B (en) | Aromatic dicarboxylic acid containing troger base and preparation method thereof | |
| CN112574148B (en) | Preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) | |
| CN108047243B (en) | 2,3,6, 7-penta-pterene tetracarboxylic dianhydride compound and synthetic method thereof | |
| CN112500297B (en) | Bis-trifluoromethyl-benzene-substituted asymmetric meta-aromatic diamine monomer and preparation method thereof | |
| CN110078922B (en) | Method for synthesizing polysulfone by using palladium-catalyzed homogeneous allyl substitution reaction | |
| CN115505100A (en) | Epoxy resin based on spirosilafluorene as skeleton and preparation method and application thereof | |
| JP2002256072A (en) | Synthesis of polyetherketone (ppek) having phthalazine structure | |
| JP2021172789A (en) | Method for producing charge-transporting polymer | |
| KR20020063073A (en) | 3,6-di(3',5'-bis(trifluoromethyl)benzene)pyromellitic dianhydride, and process for preparing them | |
| CN115583929B (en) | Preparation method of bisphenol A diether dianhydride | |
| JP4176074B2 (en) | Bisphenyl-2,3,5,6-tetrafluoro-4-trifluoromethylphenylphosphine oxide derivative and method for producing the same | |
| CN110746462A (en) | Efficient synthesis method of dendritic cyclotriphosphazene compound | |
| CN110963985B (en) | Preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride | |
| CN115536666B (en) | Dianhydride monomer containing benzobisnorbornene cyclobutane structure and preparation method and application thereof | |
| CN113234006B (en) | Method for synthesizing bismaleimide containing adamantane side group triarylamine | |
| CN1634904A (en) | Process for synthesis of aryl bis-ether dianhydrides monomer | |
| CN113480505B (en) | Method for preparing, separating and purifying biphenyl derivatives through catalytic coupling | |
| CN114349649A (en) | Two aromatic diamine monomers containing both methoxyfluorene and methyl structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |