CN111533731A - Iminicyclodiphenylamine-substituted pyridine diamine monomer and preparation method thereof, and Teleger base polymer and preparation method and application thereof - Google Patents

Iminicyclodiphenylamine-substituted pyridine diamine monomer and preparation method thereof, and Teleger base polymer and preparation method and application thereof Download PDF

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CN111533731A
CN111533731A CN202010269661.XA CN202010269661A CN111533731A CN 111533731 A CN111533731 A CN 111533731A CN 202010269661 A CN202010269661 A CN 202010269661A CN 111533731 A CN111533731 A CN 111533731A
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diphenylamine
substituted pyridine
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CN111533731B (en
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陈春海
王书丽
李莉
姚佳楠
周宏伟
赵晓刚
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Jilin University
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Abstract

The invention relates to the technical field of organic chemistry, in particular to an imine ring-containing diphenylamine substituted pyridine diamine monomer and a preparation method thereof, and a Teleger base polymer and a preparation method and application thereof. The diphenylamine substituted pyridine diamine monomer containing imine ring provided by the invention contains a rigid aromatic structure and tertiaryThe pyridine structure and the large substituent of the amino group enable the polymer of the Teller basic group obtained by self-polymerization to have a rigid aromatic structure and a V-shaped bridging structure, and the obtained polymer of the Teller basic group has high selectivity and high permeability at the same time, and is particularly suitable for CO2Has high gas permeation capacity and separation capacity.

Description

Iminicyclodiphenylamine-substituted pyridine diamine monomer and preparation method thereof, and Teleger base polymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic chemistry, in particular to an imine ring-containing diphenylamine substituted pyridine diamine monomer and a preparation method thereof, and a Teleger base polymer and a preparation method and application thereof.
Background
The gas membrane separation technology is a novel green separation technology, and compared with the traditional gas separation technology, the membrane separation technology has the advantages of high separation efficiency, simplicity in operation, low energy consumption, greenness, no pollution and the like, is a third-generation gas separation technology after cryogenic separation and pressure swing adsorption, and is widely applied to the fields of medicine and food, biochemistry, energy source environmental protection and the like. The high molecular polymer membrane has good separation performance, excellent mechanical property and physical and chemical properties, so that the high molecular polymer membrane becomes a common gas separation membrane material and is an important component of numerous applications in the membrane separation technology. At O2/N2Separation, gas dehumidification, CO2Recovery and H2The separation and recovery and the like are all important applications. However, in general, the permeability and selectivity of a polymer membrane are in a mutually restrictive relationship, i.e., the selectivity decreases as the permeability increases, which is known as the Trade-off effect. The prepared high-molecular gas separation membrane with high permeability and high selectivity has very profound influence on improving the gas separation efficiency and expanding the application range.
Polyimide is used as a high molecular polymer material with a rigid imide ring, has excellent mechanical property, high thermal stability and mechanical strength, has an adjustable pore channel structure, excellent stability, low skeleton density and a skeleton structure rich in heteroatoms such as nitrogen, oxygen and the like, and has great application prospects in the fields of gas separation and adsorption. However, the molecular chains of the polyimide materials have certain flexibility, which easily causes the collapse of the polymer framework and the tight packing between the molecular chains, so that the prepared polyimide film has low gas permeability and cannot be applied to the field of gas film separation.
Disclosure of Invention
The invention aims to provide an imine ring-containing diphenylamine substituted pyridine diamine monomer, and a gas separation membrane prepared from a Teller base polymer obtained by polymerizing the monomer provided by the invention has good selectivity and gas permeability, and is suitable for the technical field of gas separation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an imine ring-containing diphenylamine substituted pyridine diamine monomer, which has a structure shown in a formula I:
Figure BDA0002442646980000021
in the formula I, R is
Figure BDA0002442646980000022
Figure BDA0002442646980000023
AR is
Figure BDA0002442646980000024
Figure BDA0002442646980000025
Preferably, the imine ring-containing diphenylamine substituted pyridine diamine monomer comprises
Figure BDA0002442646980000031
The invention provides a preparation method of an imine ring-containing diphenylamine substituted pyridine diamine monomer, which comprises the following steps:
mixing R-CHO, acetophenone, ammonium acetate and glacial acetic acid, and carrying out addition reaction to obtain a pyridine monomer containing diphenylamine substituent;
mixing the diphenylamine-substituted pyridine-containing monomer, concentrated sulfuric acid and concentrated nitric acid, and carrying out nitration reaction to obtain a diphenylamine-substituted pyridine dinitro monomer;
mixing the diphenylamine substituted pyridine dinitro monomer, a first organic solvent, a catalyst and a reducing agent, and carrying out reduction reaction to obtain a diphenylamine substituted pyridine diamino monomer with a structure shown in a formula II;
mixing the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II, the aromatic dianhydride with the structure shown in the formula III, a second organic solvent and toluene, and carrying out substitution reaction to obtain an imine ring-containing diphenylamine substituted pyridine diamine monomer with the structure shown in the formula I;
the first organic solvent is 1, 4-dioxane or absolute ethyl alcohol; the second organic solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
Figure BDA0002442646980000041
preferably, the temperature of the addition reaction is 110-120 ℃ and the time is 2-4 h.
Preferably, the molar ratio of the diphenylamine-substituted pyridine-containing monomer to the concentrated sulfuric acid to the concentrated nitric acid is 1: (0.1-0.5): (0.2 to 0.5); the mass concentration of the concentrated nitric acid is 45%.
Preferably, the temperature of the reduction reaction is 100-110 ℃, and the time is 12-18 h.
Preferably, the substitution reaction comprises a low-temperature substitution reaction and a high-temperature substitution reaction which are sequentially carried out; the temperature of the low-temperature substitution reaction is 140-150 ℃, and the time of the low-temperature substitution reaction is 2-3 h; the temperature of the high-temperature substitution reaction is 170-200 ℃, and the time of the high-temperature substitution reaction is 7-9 hours.
The invention provides a Teleger base polymer, which is obtained by polymerizing an imine ring-containing diphenylamine substituted pyridine diamine monomer or an imine ring-containing diphenylamine substituted pyridine diamine monomer prepared by the preparation method in the technical scheme, and has a structure shown in a formula IV:
Figure BDA0002442646980000051
wherein n is an integer of 50-70.
The invention also provides a preparation method of the Teller base polymer in the technical scheme, which comprises the following steps:
mixing the imine ring-containing diphenylamine substituted pyridine diamine monomer or the imine ring-containing diphenylamine substituted pyridine diamine monomer prepared by the preparation method of the technical scheme, dimethoxymethane and trifluoroacetic acid, and carrying out polymerization reaction to obtain the Teller-Kjeldahl base polymer with the structure shown in the formula IV.
The invention also provides the application of the Teller diagram basic group polymer or the Teller diagram basic group polymer prepared by the preparation method in the technical scheme in the field of gas separation.
The imine-containing cyclic diphenylamine substituted pyridine diamine monomer contains a rigid aromatic structure, a tertiary amino pyridine structure and a large substituent (methyl, trifluoromethyl or isopropyl), so that a Teller basic group polymer obtained by self polymerization has a rigid aromatic structure and a V-shaped bridging structure, a large rigid framework is endowed to the Teller basic group polymer, the free volume of the Teller basic group polymer can be increased, and the gas permeability is further improved; the existence of the basic group tertiary amino can increase the interaction with the acid gas, improve the permeability of the acid gas and ensure good selectivity; the existence of the substituent (methyl, trifluoromethyl or isopropyl) can disturb the regularity of a polymer chain and increase the permeability of gas; through the molecular structure design, the invention ensures that the Teller's basic group polymer obtained by taking the imine ring-containing diphenylamine substituted pyridine diamine monomer as the raw material through self-polymerization has high selectivity and high permeability to acid gas, especially to CO2Has high gas permeation energyForce. In addition, the polymer of Teller base obtained by self-polymerization of the monomer containing the imine ring diphenylamine substituted pyridine diamine has excellent thermal property and solubility.
Drawings
FIG. 1 is a nuclear magnetic diagram of a diphenylamine substituted imine ring diamino monomer prepared in example 1;
FIG. 2 is a nuclear magnetic diagram of a diphenylamine substituted imine cyclomethyldiamino monomer prepared in example 2;
FIG. 3 is a nuclear magnetic diagram of a diphenylamine substituted imine cycloisopropyldiamino monomer prepared in example 3;
FIG. 4 is a nuclear magnetic diagram of a diphenylamine substituted imine cyclotrifluoromethyldiamino monomer prepared in example 4;
FIG. 5 is an IR spectrum of a Teller base polymer prepared in examples 5 to 8.
Detailed Description
The invention provides an imine ring-containing diphenylamine substituted pyridine diamine monomer, which has a structure shown in a formula I:
Figure BDA0002442646980000061
in the formula I, R is
Figure BDA0002442646980000062
Figure BDA0002442646980000063
AR is
Figure BDA0002442646980000064
Figure BDA0002442646980000065
Figure BDA0002442646980000071
In the present invention, "-" in R and AR structures denotes a linking site.
In the present invention, the imine ring-containing diphenylamine substituted pyridine diamine monomer preferably includes
Figure BDA0002442646980000072
Figure BDA0002442646980000081
The invention provides a preparation method of an imine ring-containing diphenylamine substituted pyridine diamine monomer, which comprises the following steps:
mixing R-CHO, acetophenone, ammonium acetate and glacial acetic acid, and carrying out addition reaction to obtain a pyridine monomer containing diphenylamine substituent;
mixing the diphenylamine-substituted pyridine-containing monomer, concentrated sulfuric acid and concentrated nitric acid, and carrying out nitration reaction to obtain a diphenylamine-substituted pyridine dinitro monomer;
mixing the diphenylamine substituted pyridine dinitro monomer, a first organic solvent, a catalyst and a reducing agent, and carrying out reduction reaction to obtain a diphenylamine substituted pyridine diamino monomer with a structure shown in a formula II;
mixing the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II, the aromatic dianhydride with the structure shown in the formula III, a second organic solvent and toluene, and carrying out substitution reaction to obtain an imine ring-containing diphenylamine substituted pyridine diamine monomer with the structure shown in the formula I;
Figure BDA0002442646980000082
R-CHO, acetophenone, ammonium acetate and glacial acetic acid are mixed and subjected to addition reaction to obtain the diphenylamine-substituted pyridine-containing monomer. In the present invention, R in R-CHO is identical to the above-mentioned R, and thus, detailed description thereof is omitted; in a specific embodiment of the present invention, the R-CHO is benzaldehyde, p-tolualdehyde, p-isopropylbenzaldehyde, p-trifluoromethylbenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde or 1-pyreneformaldehyde. In the invention, the molar ratio of R-CHO, acetophenone, ammonium acetate and glacial acetic acid is preferably 1 (2-4): 13-15): 40-44, and more preferably 1:3:14: (41-43).
In the invention, the mixing mode is preferably stirring, and the stirring speed is preferably 600-900 r/min, more preferably 700-800 r/min; the stirring time is preferably 3-5 h, and more preferably 4 h. In the invention, the temperature of the addition reaction is preferably 110-120 ℃; the time of the addition reaction is preferably 2 to 4 hours, more preferably 3 hours, and the time is counted from the temperature of the system rising to the temperature of the addition reaction. In the present invention, the addition reaction is preferably carried out in a nitrogen atmosphere. In the invention, glacial acetic acid is used as a catalyst and a solvent, and R-CHO, acetophenone and ammonium acetate are subjected to addition reaction under the action of the glacial acetic acid to obtain the diphenylamine-substituted pyridine monomer.
After the addition reaction, the system obtained by the addition reaction is preferably subjected to suction filtration, washing and recrystallization in sequence to obtain the diphenylamine-substituted pyridine-containing monomer. In the present invention, the washing detergent is preferably 50 wt.% acetic acid and cold ethanol, and the specific washing manner is preferably three times of alternate washing with 50 wt.% acetic acid and cold ethanol in this order. In the present invention, it is preferable that the system obtained by the addition reaction is cooled to precipitate a solid, and then the obtained solid is filtered. In the present invention, the solvent for recrystallization is preferably anhydrous methanol.
After the diphenylamine-substituted pyridine-containing monomer is obtained, the diphenylamine-substituted pyridine-containing monomer, concentrated sulfuric acid and concentrated nitric acid are mixed and subjected to nitration reaction to obtain the diphenylamine-substituted pyridine dinitro monomer. In the invention, the mass concentration of the concentrated sulfuric acid is preferably 98%; the mass concentration of the concentrated nitric acid is preferably 45%. In the present invention, the molar ratio of the diphenylamine-substituted pyridine-containing monomer to the concentrated sulfuric acid to the concentrated nitric acid is preferably 1: (0.1-0.5): (0.2 to 0.5), more preferably 1: (0.2-0.4): (0.3-0.4). In the present invention, the temperature of the mixing is preferably 0 ℃; the specific mode of mixing is preferably as follows: firstly, mixing concentrated sulfuric acid and concentrated nitric acid to obtain mixed acid; the mixed acid is then added dropwise to the diphenylamine-substituted pyridine-containing monomer. In the present invention, the dropping rate is preferably 0.01 to 0.02mL/s, and more preferably 0.015 mL/s.
In the invention, the temperature of the nitration reaction is preferably room temperature, particularly preferably 20-30 ℃, and further preferably 25 ℃; the time of the nitration reaction is preferably 10-24 h, more preferably 12-14 h, and timing is started when the concentrated sulfuric acid and the concentrated nitric acid are completely added into the diphenylamine-substituted pyridine-containing monomer. In the invention, concentrated sulfuric acid is used as a catalyst and a dehydrating agent to promote the nitration of diphenylamine substituted pyridine-containing monomers by concentrated nitric acid.
After the nitration reaction, the system obtained by the nitration reaction is preferably subjected to filtration, washing and column chromatography in sequence to obtain the diphenylamine-substituted pyridine dinitro monomer. In the embodiment of the present invention, it is preferable to add water to the system obtained by the nitration reaction, precipitate a solid, and filter it. In the present invention, the washing detergent is preferably methanol; the chromatographic column adopted by the column chromatography is preferably petroleum ether and ethyl acetate with the volume ratio of 4: 1.
After the diphenylamine-substituted pyridine dinitro monomer is obtained, the diphenylamine-substituted pyridine dinitro monomer, a first organic solvent, a catalyst and a reducing agent are mixed for reduction reaction to obtain the diphenylamine-substituted pyridine diamino monomer with the structure shown in the formula II.
In the present invention, the first organic solvent is 1, 4-dioxane or absolute ethyl alcohol; the molar ratio of the diphenylamine-substituted pyridine dinitro monomer to the first organic solvent is preferably 1 (0.5-2), and more preferably 1 (0.5-1.5). In the present invention, the catalyst is preferably palladium on carbon; the mass content of palladium in the palladium-carbon is preferably 5%; the mass ratio of the diphenylamine-substituted pyridine dinitromonomer to the catalyst is preferably 1: (0.2 to 0.5), more preferably 1: (0.3-0.4). In the present invention, the reducing agent is preferably sodium sulfide or hydrazine hydrate; the molar ratio of diphenylamine-substituted pyridine dinitromonomer to reducing agent is preferably 1: (15-20), more preferably 1: (17-18).
In the present invention, the mixing mode is specifically preferably: heating a mixed material of diphenylamine substituted pyridine dinitro monomer, a first organic solvent and a catalyst to reflux to obtain a mixed material; then, a reducing agent is added dropwise to the mixed material. In the invention, the reflux temperature is preferably 100-110 ℃, and more preferably 105-110 ℃. In the present invention, the dropping speed is preferably 0.2 to 0.6mL/min, and more preferably 0.3 to 0.5 mL/min. Before the reduction reaction, the system is heated and refluxed, which is beneficial to improving the efficiency of the reduction reaction.
In the invention, the temperature of the reduction reaction is preferably 100-110 ℃, and more preferably 105-110 ℃; the time of the reduction reaction is preferably 12-18 h, more preferably 14-16 h, and the time is counted when the temperature of the reaction system reaches the temperature of the reduction reaction. In the reduction reaction process, the nitro group on the diphenylamine substituted pyridine dinitro monomer is reduced into amino. The progress of the reduction reaction is preferably checked by TLC in the present invention.
After the reduction reaction, the system obtained by the reduction reaction is preferably subjected to filtration, filtrate concentration and recrystallization in sequence to obtain the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II. The catalyst is removed by filtration, and the specific process of concentrating and recrystallizing the filtrate is not particularly limited in the invention, and the filtrate concentrating and recrystallizing process known to those skilled in the art can be adopted. In the present invention, the solvent for recrystallization is preferably ethanol.
In the invention, the synthesis reaction formula of the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II is shown as follows:
Figure BDA0002442646980000111
after the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II is obtained, the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II, the aromatic dianhydride with the structure shown in the formula III, a second organic solvent and toluene are mixed for substitution reaction, and the imine ring-containing diphenylamine substituted pyridine diamine monomer with the structure shown in the formula I is obtained.
In the present invention, AR in the aromatic dianhydride having the structure represented by formula iii is as described above, and is not described herein again; in a specific embodiment of the present invention, the aromatic dianhydride having the structure represented by formula III is pyromellitic dianhydride, s-biphenyltetracarboxylic dianhydride, a-biphenyltetracarboxylic dianhydride, i-biphenyltetracarboxylic dianhydride, 4' - (hexafluoroisopropylene) diphthalic anhydride, s-diphenylethertetracarboxylic dianhydride, a-diphenylethertetracarboxylic dianhydride, i-diphenylethertetracarboxylic dianhydride, s-benzophenonetetracarboxylic dianhydride, a-benzophenonetetracarboxylic dianhydride, or i-benzophenonetetracarboxylic dianhydride. In the invention, the molar ratio of the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II to the aromatic dianhydride with the structure shown in the formula III is preferably (3-4): 1, more preferably 3.5: 1. In the present invention, the second organic solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the molar ratio of the aromatic dianhydride represented by the formula III to the second organic solvent is preferably 1 (0.1-1), and more preferably 1 (0.15-0.5). In the invention, the molar ratio of the aromatic dianhydride represented by the formula III to the toluene is preferably 1 (0.05-1), and more preferably 1 (0.06-0.08).
In the invention, the mixing is preferably carried out under the condition of stirring, and the stirring speed is preferably 800-900 r/min; the stirring time is preferably 0.5 h; the specific mode of mixing is preferably as follows: firstly, aromatic dianhydride with a structure shown in a formula III and a first organic solvent are mixed for the first time to obtain an aromatic dianhydride solution; and then mixing the aromatic dianhydride solution, diphenylamine substituted pyridine diamino monomer with a structure shown in a formula II and toluene for the second time.
In the present invention, the substitution reaction preferably includes a low-temperature substitution reaction and a high-temperature substitution reaction which are sequentially performed; the temperature of the low-temperature substitution reaction is preferably 140-150 ℃, and more preferably 142-148 ℃; the time of the low-temperature substitution reaction is preferably 2-3 h, and more preferably 2.5 h; the temperature of the high-temperature substitution reaction is preferably 170-200 ℃, and more preferably 180-190 ℃; the time of the high-temperature substitution reaction is preferably 7-9 h, and more preferably 8 h. The invention removes water and residual toluene generated in the reaction process through low-temperature substitution reaction; the reaction is carried out more thoroughly through the high-temperature substitution reaction. In the invention, the heating rate from room temperature to the temperature of the low-temperature substitution reaction is preferably 5-10 ℃/min, and more preferably 8 ℃/min; the heating rate from the temperature of the low-temperature substitution reaction to the temperature of the high-temperature substitution reaction is preferably 7-12 ℃/min, and more preferably 9 ℃/min. The invention adopts the heating rate to ensure complete reaction on the basis of full contact.
After the substitution reaction, the obtained system is preferably cooled to room temperature, and then is sequentially filtered and recrystallized. In the embodiment of the present invention, it is preferable that a mixture of deionized water and methanol is added to the system obtained by the substitution reaction, and a solid is precipitated and filtered; the volume ratio of the deionized water to the methanol is preferably 1: 1. In the present invention, the solution used for recrystallization is preferably a mixed solution of ethanol and water; the volume ratio of ethanol to water is preferably 1: 1.
In the invention, the reaction formula of synthesizing the diphenylamine substituted pyridine diamine monomer with the structure shown in the formula I from the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II and the aromatic dianhydride with the structure shown in the formula III is shown as follows:
Figure BDA0002442646980000121
the invention also provides a Teleger base polymer which is obtained by polymerizing the diphenylamine substituted pyridine diamine monomer containing imine rings according to the technical scheme and has a structure shown in a formula IV:
Figure BDA0002442646980000131
wherein n is an integer of 50-70, preferably an integer of 55-65; "-" indicates the attachment site.
In a specific embodiment of the invention, the polymer of Teller bases comprises:
Figure BDA0002442646980000132
wherein n is 50-70, and the number average molecular weight is (5-9) × 104；
Figure BDA0002442646980000133
Wherein n is 50-65, and the number average molecular weight is (5-8.5) × 104；
Figure BDA0002442646980000134
Wherein n is 60-70, and the number average molecular weight is (7-9) × 104(ii) a Or
Figure BDA0002442646980000141
Wherein n is 50-80, and the number average molecular weight is (6-10) × 104。
In the invention, the existence of a rigid aromatic structure and a V-shaped bridging structure in the Teller-Kwangsi base polymer endows the Teller-Kwangsi base polymer with a large rigid skeleton, so that the free volume of the Teller-Kwangsi base polymer is improved, the gas permeability is further improved, the interaction with acid gas can be increased due to the existence of a basic group tertiary amino group, and the permeability and selectivity of the acid gas are improved; the existence of a plurality of tertiary amino groups can increase the interaction with an organic solvent, and the problem that most glassy polymers are difficult to dissolve is solved; the presence of the substituent (methyl, trifluoromethyl or isopropyl) can disturb the regularity of polymer chains, increase the gas permeability and the permeability of organic solvents, improve the problem of poor solubility of conventional gas separation membranes due to rigid chains, and can improve the gas permeability thereof.
The invention provides a preparation method of the Teller base polymer in the technical scheme, which comprises the following steps:
mixing the imine ring-containing diphenylamine substituted pyridine diamine monomer, dimethoxymethane and trifluoroacetic acid, and carrying out polymerization reaction to obtain the Teller-Kwangsi base polymer with the structure shown in formula IV.
In the invention, the mol ratio of the imine ring-containing diphenylamine substituted pyridine diamine monomer to the dimethoxymethane to the trifluoroacetic acid is preferably 1 (5-7) to (100-120); more preferably 1:6 (105-110). In the present invention, the specific manner of mixing is preferably: dissolving the imine ring-containing diphenylamine substituted pyridine diamine monomer in dimethoxymethane, and then dropwise adding trifluoroacetic acid into the obtained solution. In the present invention, the temperature of the solution during the dropping is preferably 0 ℃; the dropping speed is preferably 0.01-0.04 mL/min, and more preferably 0.02-0.03 mL/s.
In the invention, the temperature of the polymerization reaction is preferably room temperature, particularly preferably 20-30 ℃, and further preferably 25 ℃; the time of the polymerization reaction is preferably 12-24 hours, and more preferably 16-20 hours. In the present invention, the polymerization reaction is preferably carried out in a nitrogen atmosphere. In the invention, under the action of trifluoroacetic acid, imine ring-containing diphenylamine substituted pyridine diamine monomer and dimethoxymethane monomer are polymerized to generate polymer containing a Teleger base structure.
After the polymerization reaction, a viscous polymer solution is obtained, the pH value of the obtained system is preferably adjusted to 9, and a solid is precipitated; and then washing, purifying, filtering and drying the precipitated solid polymer in sequence to obtain the Teller-Kwangsi base polymer with the structure shown in the formula IV. In the invention, the preferable reagent for adjusting the pH value of the system obtained by the polymerization reaction is ammonia water, and the preferable mass concentration of the ammonia water is 25-28%. The invention can alkalize the system and neutralize redundant trifluoroacetic acid by adjusting the pH value. In the present invention, the washing is preferably performed 3 times by alternately washing with deionized water and acetone. In the present invention, the specific process of the purification is preferably: and dissolving the washed polymer in chloroform, and adding n-hexane to separate out a solid. The filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used. In the present invention, the drying is preferably vacuum drying; the temperature of the drying is preferably 100 ℃; the drying time is preferably 12 h; the vacuum degree of the vacuum drying is preferably-0.1 MPa.
The invention also provides application of the Teller basic group polymer in the technical scheme in the field of gas separation, and the application is particularly applied to separation of acid gas such as CO2A gas. In the embodiment of the present invention, the polymer film of the Teller base polymer is preferably prepared for gas separation. In the present invention, the method for preparing the polymer film preferably includes: dissolving the Teller-G base polymer in chloroform to obtain a polymer solution; and then coating the polymer solution on the surface of a matrix by adopting a scraper, and drying to obtain the polymer film. In the present invention, the solid content of the polymer solution is preferably 15%; in the embodiment of the present invention, it is preferable that the polymer solution is obtained by dissolving the polymer of Teller's bases in chloroform, and then filtering the resulting solution through a 0.45 μm Teflon filter to remove insoluble substances. In the present invention, the substrate is preferably a glass plate. In the present invention, the thickness of the coating is preferably 50 to 80 μm, and more preferably 60 to 70 μm. In the present invention, the drying procedure is preferably: drying for 12h at 60 ℃; then dried at 90 ℃ for 4 h.
The invention firstly synthesizes diamino monomer containing imine ring, then synthesizes rigid Teller base polymer structure, compared with polyimide synthesized by traditional method, the invention greatly improves the permeability of gas in polymer film, and CO exists due to the basic group tertiary amino in the Teller base polymer structure2The molecule has strong C ═ O dipole bond, can form quadrupole moment, and the polar unit tertiary amino in the polymer can react with CO2Polar interaction of (2) increasing Polymer to CO2Thereby increasing the dissolving capacity of CO2The permeability of the gas.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 30mmol of benzaldehyde, 60mmol of acetophenone, 30g of ammonium acetate and 75mL of glacial acetic acid into a three-neck flask provided with a mechanical stirring device, reacting for half an hour at room temperature under the protection of nitrogen, heating a system to 120 ℃, carrying out addition reaction for 4 hours, cooling to separate out a solid, filtering, and alternately washing with 50 wt.% of acetic acid and cold ethanol (at the temperature of 0 ℃) for three times to obtain a crude product; recrystallizing the crude product from anhydrous methanol to obtain a product, filtering and drying to obtain a diphenylamine-substituted pyridine monomer;
adding 10mmol of diphenylamine-substituted pyridine-containing monomer into a three-neck flask provided with a mechanical stirring device, maintaining the temperature of the system at 0 ℃, dropwise adding a mixed acid consisting of 2mL of concentrated sulfuric acid (with the mass concentration of 98%) and 6mL of 45 wt% concentrated nitric acid into the reaction system, carrying out nitration reaction at room temperature under the protection of nitrogen gas in the reaction system overnight, separating out a solid, and filtering; then petroleum ether and ethyl acetate with the volume ratio of 4:1 are used for column chromatography and purification to obtain diphenylamine substituted pyridine dinitro monomer; the structural formula of the obtained diphenylamine-substituted pyridine dinitro monomer is shown as follows:
Figure BDA0002442646980000161
adding 8mmol of diphenylamine substituted pyridine dinitro monomer, 57mL of 1, 4-dioxane and 1.5g of palladium carbon (the content of palladium is 5 wt.%) into a three-neck flask provided with a mechanical stirring device, maintaining the solid content of a reaction system to be 5%, heating the temperature of the reaction system to 115 ℃ for reflux, dropwise adding 160mmol of hydrazine hydrate into the reaction system, carrying out reduction reaction for 12 hours, filtering while hot to remove the palladium carbon, collecting filtrate, cooling to separate out solid, filtering, recrystallizing with ethanol, and drying to obtain diphenylamine substituted pyridine diamino monomer; the structural formula of the diphenylamine substituted pyridine diamino monomer is shown as follows:
Figure BDA0002442646980000171
adding 2mmol of 4,4'- (hexafluoroisopropylene) diphthalic anhydride and 25mLN, N-dimethylformamide into a three-neck flask provided with a mechanical stirring device, controlling the solid content of a reaction system to be 10%, adding 6mmol of diphenylamine substituted pyridine diamino monomer and 15mL of toluene after 4,4' - (hexafluoroisopropylene) diphthalic anhydride is completely dissolved, heating the reaction system to 150 ℃, removing all water generated by the reaction, evaporating the residual toluene, heating the reaction system to 180 ℃, maintaining the substitution reaction for 12 hours, stopping the reaction, placing the reaction mixture in a mixture of deionized water and methanol, separating out a solid, filtering, recrystallizing ethanol/water, and drying to obtain diphenylamine substituted imine cyclic diamino monomer; the structural formula of the diphenylamine substituted imine ring diamino monomer is shown as follows:
Figure BDA0002442646980000172
the yield of the diphenylamine substituted imine ring diamino monomer is 92 percent;
the nuclear magnetic diagram of the diphenylamine substituted imine cyclic diamino monomer obtained in example 1 is shown in FIG. 1; as can be seen from the characteristic peaks in FIG. 1, the diphenylamine substituted imine ring diamino monomer is successfully prepared by the invention.
Example 2
Adding 30mmol of p-tolualdehyde, 60mmol of acetophenone, 30g of ammonium acetate and 75mL of glacial acetic acid into a three-neck flask provided with a mechanical stirring device, reacting for half an hour at room temperature under the protection of nitrogen, heating a system to 120 ℃, carrying out addition reaction for 5 hours, cooling to separate out a solid, filtering, and alternately washing with 50 wt.% of acetic acid and cold ethanol (the temperature is 0 ℃) for three times to obtain a crude product; recrystallizing the crude product from anhydrous methanol to obtain a product, filtering and drying to obtain a monomer containing diphenylamine substituted methylpyridine;
adding 10mmol of diphenylamine substituted methylpyridine monomer into a three-neck flask provided with a mechanical stirring device, maintaining the temperature of the system at 0 ℃, dropwise adding a mixed acid consisting of 2mL of concentrated sulfuric acid (with the mass concentration of 98%) and 6mL of 45 wt% concentrated nitric acid into the reaction system, reacting the reaction system at room temperature overnight under the protection of nitrogen, separating out a solid, and filtering; petroleum ether and ethyl acetate in a volume ratio of 4:1 are adopted for column chromatography and purification to obtain diphenylamine substituted picolyl dinitro monomer; the structural formula of the diphenylamine substituted picolyl dinitro monomer is shown as follows:
Figure BDA0002442646980000181
adding 8mmol of diphenylamine substituted picolyl dinitro monomer, 28mL of 1, 4-dioxane and 1.5g of palladium carbon (the content of palladium is 5 wt.%) into a three-neck flask provided with a mechanical stirring device, maintaining the solid content of a reaction system to be 8%, heating the temperature of the reaction system to 110 ℃ for reflux, dropwise adding 120mmol of hydrazine hydrate into the reaction system, carrying out reduction reaction for 12 hours, filtering while hot to remove the palladium carbon, collecting filtrate, cooling to separate out solid, filtering, recrystallizing with ethanol, and drying to obtain diphenylamine substituted picolyl diamino monomer; the structural formula of the diphenylamine substituted picolyl diamino monomer is shown as follows:
Figure BDA0002442646980000182
adding 2mmol of 4,4'- (hexafluoroisopropylene) diphthalic anhydride and 25mLN, N-dimethylformamide into a three-neck flask provided with a mechanical stirring device, controlling the solid content of a reaction system to be 10%, adding 6mmol of diphenylamine substituted picolyl diamino monomer and 15mL of toluene after 4,4' - (hexafluoroisopropylene) diphthalic anhydride is completely dissolved, heating the reaction system to 150 ℃, completely taking out water generated by the reaction, distilling out the residual toluene, heating the reaction system to 180 ℃, maintaining the reaction for 12 hours, stopping the reaction, placing the reaction mixture into a mixture of deionized water and methanol, separating out a solid, filtering, recrystallizing ethanol/water, and drying to obtain diphenylamine substituted imine cyclomethyl diamino monomer: the structural formula of the diphenylamine substituted imine cyclomethiodiamino monomer is shown as follows:
Figure BDA0002442646980000191
the yield of the diphenylamine substituted imine cyclomethiodiamino monomer is 94 percent;
the nuclear magnetic diagram of the diphenylamine substituted imine cyclomethiodiamino monomer obtained in example 2 is shown in FIG. 2; as can be seen from the characteristic peaks in FIG. 2, the diphenylamine substituted imine cyclomethiodiamino monomer is successfully prepared by the method.
Example 3
Adding 30mmol of p-isopropyl benzaldehyde, 60mmol of acetophenone, 30g of ammonium acetate and 75mL of glacial acetic acid into a three-neck flask provided with a mechanical stirring device, reacting for half an hour at room temperature under the protection of nitrogen, heating a system to 120 ℃, carrying out addition reaction for 4 hours, cooling to separate out a solid, filtering, and alternately washing with 50 wt.% of acetic acid and cold ethanol (at the temperature of 0 ℃) for three times to obtain a crude product; recrystallizing the crude product from anhydrous methanol to obtain a product, filtering and drying to obtain a monomer containing diphenylamine substituted isopropyl pyridine;
adding 10mmol of diphenylamine substituted isopropylpyridine dinitro monomer into a three-neck flask provided with a mechanical stirring device, maintaining the temperature of the system at 0 ℃, dropwise adding a mixed acid consisting of 2mL of concentrated sulfuric acid (with the mass concentration of 98%) and 6mL of 45 wt% concentrated nitric acid into the reaction system, fully introducing nitrogen for protection, reacting the reaction system at room temperature overnight, separating out a solid, and filtering; passing the mixture through a column by using n-hexane and ethyl acetate in a volume ratio of 2:1, and purifying to obtain diphenylamine substituted pyridine isopropyl dinitro monomer; the structural formula of the diphenylamine substituted pyridine isopropyl dinitro monomer is shown as follows:
Figure BDA0002442646980000201
adding 8mmol of diphenylamine substituted pyridine isopropyl dinitro monomer, 60mL of 1, 4-dioxane and 1.5g of palladium-on-carbon (the content of palladium is 5 wt.%) into a three-neck flask provided with a mechanical stirring device, maintaining the solid content of a reaction system to be 5%, heating the temperature of the reaction system to reflux, adding 120mmol of sodium sulfide into the reaction mixture, reacting for 16 hours, filtering while hot to remove palladium-carbon, collecting filtrate, cooling to separate out solid, filtering, recrystallizing with methanol, and drying to obtain diphenylamine substituted pyridine isopropyl diamino monomer; the structural formula of the diphenylamine substituted pyridine isopropyl diamino monomer is shown as follows:
Figure BDA0002442646980000202
adding 2mmol of 4,4'- (hexafluoroisopropylidene) diphthalic anhydride and 25mLN, N-dimethylformamide into a three-neck flask provided with a mechanical stirring device, controlling the solid content of a reaction system to be 10%, adding 6mmol of diphenylamine substituted pyridine isopropyldiamino monomer and 20mL of toluene after 4,4' - (hexafluoroisopropylidene) diphthalic anhydride is completely dissolved, heating the reaction system to 150 ℃, completely taking out water generated by reaction, evaporating residual toluene, heating the system to 180 ℃, maintaining the substitution reaction for 13 hours, stopping the reaction, placing the reaction mixture into a mixture of deionized water and methanol, separating out a solid, filtering, recrystallizing ethanol/water, and drying to obtain diphenylamine substituted imine cyclo-isopropyldiamino monomer; the structural formula of the diphenylamine substituted imine cycloisopropyl diamino monomer is shown as follows:
Figure BDA0002442646980000211
the yield of the diphenylamine substituted imine cycloisopropyl diamino monomer is 90 percent;
the nuclear magnetic diagram of the diphenylamine substituted imine cycloisopropyl diamino monomer obtained in example 3 is shown in FIG. 3; as can be seen from the characteristic peaks in FIG. 3, the diphenylamine substituted imine cycloisopropyl diamino monomer is successfully prepared by the method.
Example 4
Adding 30mmol of p-trifluoromethylbenzaldehyde, 60mmol of acetophenone, 30g of ammonium acetate and 75mL of glacial acetic acid into a three-neck flask provided with a mechanical stirring device, reacting for half an hour at room temperature under the protection of nitrogen, heating a system to 110 ℃, reacting for 3 hours, cooling to separate out a solid, filtering, and alternately washing for three times by sequentially using 50 wt.% of acetic acid and cold ethanol (the temperature is 0 ℃) to obtain a crude product; recrystallizing the crude product from anhydrous methanol to obtain a product, filtering and drying to obtain a diphenylamine-substituted trifluoromethyl pyridine monomer;
adding 10mmol of diphenylamine substituted trifluoromethyl pyridine dinitro monomer into a three-neck flask provided with a mechanical stirring device, maintaining the temperature of the system at 0 ℃, dropwise adding 8mL of mixed acid (2mL of concentrated sulfuric acid and 6mL of 45 wt.% concentrated nitric acid) into the reaction system, reacting the reaction system at room temperature overnight under the protection of nitrogen, separating out a solid, and filtering; passing normal hexane and methanol in a volume ratio of 2:1 through a column, and purifying to obtain diphenylamine substituted pyridine trifluoromethyl dinitro monomer; the structural formula of the diphenylamine substituted pyridine trifluoromethyl dinitro monomer is shown as follows:
Figure BDA0002442646980000212
adding 8mmol of diphenylamine substituted pyridine trifluoromethyl dinitro monomer, 35mL of 1, 4-dioxane and 1.5g of palladium carbon (the content of palladium is 5 wt.%) into a three-neck flask provided with a mechanical stirring device, maintaining the solid content of a reaction system to be 10%, heating the temperature of the reaction system to reflux, adding 120mmol of sodium sulfide into the reaction mixture, reacting for 16 hours, filtering while hot to remove the palladium carbon, collecting filtrate, cooling to separate out solid, filtering, recrystallizing a methanol and ethanol mixture (the volume ratio is 1:1), and drying to obtain the diphenylamine substituted pyridine trifluoromethyl diamino monomer; the structural formula of the diphenylamine substituted pyridine trifluoromethyl diamino monomer is shown as follows:
Figure BDA0002442646980000221
adding 2mmol of 4,4'- (hexafluoroisopropylene) diphthalic anhydride and 28mLN, N-dimethylformamide into a three-neck flask provided with a mechanical stirring device, controlling the solid content of a reaction system to be 10%, adding 6mmol of diphenylamine substituted pyridine trifluoromethyl diamino monomer and 20mL of toluene after 4,4' - (hexafluoroisopropylene) diphthalic anhydride is completely dissolved, heating the reaction system to 150 ℃, completely taking out water generated by reaction, distilling out residual toluene, heating the reaction system to 180 ℃, maintaining the reaction for 12 hours, stopping the reaction, placing the reaction mixture in a mixture of deionized water and ethanol, separating out a solid, filtering, recrystallizing methanol/water, and drying to obtain diphenylamine substituted imine ring trifluoromethyl diamino monomer; the structural formula of the obtained diphenylamine substituted imine ring trifluoromethyl diamino monomer is shown as follows:
Figure BDA0002442646980000222
the yield of the obtained diphenylamine substituted imine ring trifluoromethyl diamino monomer is 92 percent;
the nuclear magnetic diagram of the diphenylamine substituted imine trifluoromethyl diamino monomer obtained in example 4 is shown in FIG. 4; as can be seen from the characteristic peaks in FIG. 4, the diphenylamine substituted imine ring trifluoromethyl diamino monomer is successfully prepared by the invention.
Example 5
Adding 5.6mmol of dimethoxymethane and 1mmol of diphenylamine-substituted imine ring diamino monomer prepared in example 1 into a three-neck flask provided with a mechanical stirring device, controlling the temperature of a reaction system to be 0 ℃ after the diphenylamine-substituted imine ring diamino monomer is completely dissolved, dropwise adding 120mmol of trifluoroacetic acid into the reaction system, heating to the reaction temperature of 25 ℃, continuing to react for 12 hours, stopping the reaction, discharging in an ice water bath, filtering, and alternately washing with ethanol and acetone; then dissolving the solid product in trichloromethane, adding normal hexane, separating out solid, filtering, and carrying out vacuum drying to obtain diphenylamine substituted imine ring Teller base polymer, which is marked as TB-1; the structural formula of the obtained TB-1 is shown as follows:
Figure BDA0002442646980000231
wherein n is 50-70, and the number average molecular weight is (5-9) × 104。
Example 6
Adding 5.6mmol of dimethoxymethane and 1mmol of diphenylamine-substituted imine cyclomethyldiamino monomer prepared in example 2 into a three-neck flask provided with a mechanical stirring device, controlling the temperature of a reaction system to be 0 ℃ after the diphenylamine-substituted imine cyclomethyldiamino monomer is completely dissolved, dropwise adding 120mmol of trifluoroacetic acid into the reaction system, heating to the reaction temperature of 25 ℃, continuing to react for 12 hours, stopping the reaction, discharging the material into an ice water bath, filtering, and alternately washing with ethanol and acetone; then dissolving the solid product in trichloromethane, adding normal hexane, separating out solid, filtering, and carrying out vacuum drying to obtain diphenylamine substituted imine cyclomethine Teller base polymer, which is marked as TB-2; the structural formula of the obtained TB-2 is shown as follows:
Figure BDA0002442646980000232
wherein n is 50-65, and the number average molecular weight is (5-8.5) × 104。
Example 7
Adding 5.6mmol of dimethoxymethane and 1mmol of diphenylamine-substituted imine cycloisopropyldiamino monomer prepared in example 3 into a three-neck flask provided with a mechanical stirring device, controlling the temperature of a reaction system to be 0 ℃ after the diphenylamine-substituted imine cycloisopropyldiamino monomer is completely dissolved, dropwise adding 120mmol of trifluoroacetic acid into the reaction system, heating to the reaction temperature of 25 ℃, continuing to react for 12 hours, stopping the reaction, discharging the material into an ice water bath, filtering, and alternately washing with ethanol and acetone; then dissolving the solid product in trichloromethane, adding normal hexane, separating out solid, filtering, and carrying out vacuum drying to obtain diphenylamine substituted imine cycloisopropyl Teller base polymer, which is marked as TB-3; the structural formula of the obtained TB-3 is shown as follows:
Figure BDA0002442646980000241
wherein n is 60-70, and the number average molecular weight is (7-9) × 104。
Example 8
To a three-necked flask equipped with a mechanical stirring device, 5.6mmol of dimethoxymethane, 1mmol, was added
After the diphenylamine substituted imine ring trifluoromethyl diamino monomer prepared in the embodiment 4 is completely dissolved, controlling the temperature of a reaction system to be 0 ℃, dropwise adding 120mmol of trifluoroacetic acid into the reaction system, heating to the reaction temperature of 25 ℃, continuing to react for 12 hours, stopping the reaction, discharging in an ice-water bath, filtering, and alternately washing with ethanol and acetone; then dissolving the solid product in trichloromethane, adding normal hexane, separating out solid, filtering, and carrying out vacuum drying to obtain diphenylamine substituted imine trifluoromethyl Teller base polymer, which is marked as TB-4; the structural formula of the TB-4 is shown as follows:
Figure BDA0002442646980000242
wherein n is 50-80, and the number average molecular weight is (6-10) × 104。
Test example 1
The infrared spectrum of the Teller's base polymer prepared in examples 5 to 8 is shown in FIG. 5, and it can be seen from FIG. 5 that the Teller's base polymer having a rigid aromatic structure and a V-shaped bridging structure is successfully prepared by the present invention.
Test example 2
The solubility test method of the Teller base polymers prepared in examples 5 to 8 was as follows: 10mg of the Teller's base polymer prepared in examples 5 to 8 were respectively dissolved in 1mL of a solvent to be tested, N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and chloroform (CHCl), respectively, and weighed at room temperature3) In (3), the dissolution of the polymer of Teller's bases is observed; the results obtained are shown in table 1;
TABLE 1 solubility results for Teller base polymers prepared in examples 5 to 8
Figure BDA0002442646980000251
Note: the concentration of the solution for testing the solubility is 10 mg/mL; "+ +" indicates complete dissolution at room temperature.
As can be seen from Table 1, the Teller base polymer prepared by the present invention has excellent solubility. In the invention, as a plurality of tertiary amino groups are introduced into the skeleton of the Teller-Gebase polymer, the interaction with an organic solvent can be increased, and the problem that most glassy polymers are difficult to dissolve is solved; the existence of the large substituent (methyl, trifluoromethyl or isopropyl) can disturb the regularity of a polymer chain, increase the permeability of an organic solvent and have good solubility in the organic solvent.
Test example 3
Respectively dissolving the Teller-Kjeldahl base polymers prepared in examples 5-8 in chloroform at a solid content of 15%, filtering the solution by a 0.45-micron Teflon filter to remove insoluble substances to obtain a uniform Teller-Kjeldahl base polymer solution, uniformly coating the Teller-Kjeldahl base polymer on a clean 9cm × 9cm glass plate by using a scraper, drying the glass plate in a vacuum oven according to a program of 60 ℃/12h and 90 ℃/4h, and naturally cooling to obtain a polymer film;
the gas permeability properties of the polymer films obtained in examples 5 to 8 were tested by a pressure difference method (constant volume pressure method): in the testing process, the polymer film obtained in the embodiment 5-8 is sealed in a testing pool by using epoxy resin, the upstream pressure is set to be 2atm, the downstream is vacuumized, after the downstream pressure is stabilized for a period of time, the testing is carried out at 35 ℃, the separation effect of the polymer film on a gas group is represented by a gas permeability coefficient (P), and alpha represents the selectivity of ideal gas; the results obtained are shown in Table 2;
TABLE 2 results of testing of Teller base polymers prepared in examples 5-8 in gas separation
Figure BDA0002442646980000261
As can be seen from Table 2, the Teller's base polymer prepared by the invention has good selectivity and gas permeability, and can effectively separate CO2/N2、CO2/CH4And O2/N2。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. An imine ring-containing diphenylamine substituted pyridine diamine monomer has a structure shown in a formula I:
Figure FDA0002442646970000011
in the formula I, R is
Figure FDA0002442646970000012
Figure FDA0002442646970000013
AR is
Figure FDA0002442646970000014
Figure FDA0002442646970000015
2. The iminium ring-containing diphenylamine-substituted pyridine diamine monomer of claim 1, wherein the iminium ring-containing diphenylamine-substituted pyridine diamine monomer comprises
Figure FDA0002442646970000021
3. A process for preparing an imine ring-containing diphenylamine-substituted pyridine diamine monomer according to claim 1 or 2, comprising the steps of:
mixing R-CHO, acetophenone, ammonium acetate and glacial acetic acid, and carrying out addition reaction to obtain a pyridine monomer containing diphenylamine substituent;
mixing the diphenylamine-substituted pyridine-containing monomer, concentrated sulfuric acid and concentrated nitric acid, and carrying out nitration reaction to obtain a diphenylamine-substituted pyridine dinitro monomer;
mixing the diphenylamine substituted pyridine dinitro monomer, a first organic solvent, a catalyst and a reducing agent, and carrying out reduction reaction to obtain a diphenylamine substituted pyridine diamino monomer with a structure shown in a formula II;
mixing the diphenylamine substituted pyridine diamino monomer with the structure shown in the formula II, the aromatic dianhydride with the structure shown in the formula III, a second organic solvent and toluene, and carrying out substitution reaction to obtain an imine ring-containing diphenylamine substituted pyridine diamine monomer with the structure shown in the formula I;
the first organic solvent is 1, 4-dioxane or absolute ethyl alcohol; the second organic solvent is N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide;
Figure FDA0002442646970000031
4. the preparation method according to claim 3, wherein the temperature of the addition reaction is 110-120 ℃ and the time is 2-4 h.
5. The preparation method according to claim 3, wherein the molar ratio of diphenylamine-substituted pyridine-containing monomer to concentrated sulfuric acid to concentrated nitric acid is 1: (0.1-0.5): (0.2 to 0.5); the mass concentration of the concentrated nitric acid is 45%.
6. The preparation method according to claim 3, wherein the temperature of the reduction reaction is 100 to 110 ℃ and the time is 12 to 18 hours.
7. The production method according to claim 3, wherein the substitution reaction comprises a low-temperature substitution reaction and a high-temperature substitution reaction which are carried out in this order; the temperature of the low-temperature substitution reaction is 140-150 ℃, and the time of the low-temperature substitution reaction is 2-3 h; the temperature of the high-temperature substitution reaction is 170-200 ℃, and the time of the high-temperature substitution reaction is 7-9 hours.
8. A polymer of telange base, which is obtained by polymerizing the diphenylamine-substituted pyridine diamine monomer containing imine ring according to claim 1 or 2 or the diphenylamine-substituted pyridine diamine monomer containing imine ring prepared by the preparation method according to any one of claims 3 to 7, and has a structure shown in formula iv:
Figure FDA0002442646970000041
wherein n is an integer of 50-70.
9. The method for producing the polymer of Teller base according to claim 8, comprising the steps of:
mixing the imine ring-containing diphenylamine substituted pyridine diamine monomer according to claim 1 or 2 or the imine ring-containing diphenylamine substituted pyridine diamine monomer prepared by the preparation method according to any one of claims 3 to 7, dimethoxymethane and trifluoroacetic acid, and carrying out polymerization reaction to obtain the Teller-Gebase polymer with the structure shown in formula IV.
10. Use of the polymer of Teller gubasic group according to claim 8 or the polymer of Teller gubo basic group prepared by the method according to claim 9 in the field of gas separation.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112898568A (en) * 2021-02-06 2021-06-04 台州学院 Conjugated microporous polymer based on 1,3,6, 8-tetra (4-aminophenyl) pyrene and preparation method thereof
CN113549008A (en) * 2021-07-20 2021-10-26 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, Teleger base polymer, preparation and application thereof
US20220023804A1 (en) * 2018-09-17 2022-01-27 King Abdullah University Of Science And Technology Intrinsically microporous ladder-type tröger's base polymers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103846023A (en) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 Copolymerization polyimide gas separation membrane material, preparation method and application of copolymerization polyimide gas separation membrane material
CN105289337A (en) * 2015-11-04 2016-02-03 中国科学院山西煤炭化学研究所 Crosslinking polyimide gas separation membrane and preparation method
CN106279685A (en) * 2015-05-28 2017-01-04 中国科学院苏州纳米技术与纳米仿生研究所 Polyimide material, its preparation method and application of based on Teller lattice alkali structure
CN108102097A (en) * 2018-01-22 2018-06-01 吉林大学 A kind of polyimides of base containing benzyne, preparation method and applications

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103846023A (en) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 Copolymerization polyimide gas separation membrane material, preparation method and application of copolymerization polyimide gas separation membrane material
CN106279685A (en) * 2015-05-28 2017-01-04 中国科学院苏州纳米技术与纳米仿生研究所 Polyimide material, its preparation method and application of based on Teller lattice alkali structure
CN105289337A (en) * 2015-11-04 2016-02-03 中国科学院山西煤炭化学研究所 Crosslinking polyimide gas separation membrane and preparation method
CN108102097A (en) * 2018-01-22 2018-06-01 吉林大学 A kind of polyimides of base containing benzyne, preparation method and applications

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
STN: "《STN》", 28 November 2020 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220023804A1 (en) * 2018-09-17 2022-01-27 King Abdullah University Of Science And Technology Intrinsically microporous ladder-type tröger's base polymers
US11850557B2 (en) * 2018-09-17 2023-12-26 King Abdullah University Of Science And Technology Intrinsically microporous ladder-type Tröger's base polymers
CN112898568A (en) * 2021-02-06 2021-06-04 台州学院 Conjugated microporous polymer based on 1,3,6, 8-tetra (4-aminophenyl) pyrene and preparation method thereof
CN113549008A (en) * 2021-07-20 2021-10-26 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, Teleger base polymer, preparation and application thereof
CN113549008B (en) * 2021-07-20 2023-02-24 吉林大学 Diamine monomer containing aryl substituted pyridine structure, preparation and application thereof, teleger base polymer, preparation and application thereof

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