CN109232892B - Cross-linkable hyperbranched polyimide and preparation method and application thereof - Google Patents
Cross-linkable hyperbranched polyimide and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses cross-linked hyperbranched polyimide and a preparation method and application thereof, belonging to the technical field of preparation of cross-linked hyperbranched polyimide. 4, 4' - (phenylethynyl-p-phenyl) diether dianhydride is used as dicarboxylic anhydride and aromatic polyamine to prepare anhydride-terminated or amino-terminated hyperbranched polyimide, the side chain of the polymer contains crosslinkable phenylethynyl groups, and a stable space network pore channel structure is formed through thermal crosslinking, so that the polymer has a great application prospect in the field of gas adsorption materials. Compared with CN104478838A, the method has the characteristics of small pore size distribution, larger micropore volume and better gas adsorption effect, and further expands the application of the crosslinked polyimide in the field of gas adsorption materials.
Description
Technical Field
The invention belongs to the technical field of preparation of cross-linked hyperbranched polyimide.
Background
Polyimide as a special engineering plastic has excellent comprehensive properties such as good heat resistance and low temperature resistance, outstanding mechanical properties, excellent dimensional stability, good chemical stability and the like, and is widely applied to the related fields of aerospace, gas adsorption materials, microelectronic devices, coatings and the like. In addition, the hyperbranched polyimide has a multi-dimensional space network structure, so that the hyperbranched polyimide is more applied to the fields of gas adsorption and the like.
The self-crosslinking polyimide does not need to be added with a crosslinking agent, and the self active groups of the polymer react to form a crosslinking structure under certain initiation conditions. Compared with an external crosslinking agent, the self-crosslinking controllability is stronger. According to different initiation modes, the method can be divided into ultraviolet initiation and thermal initiation self-crosslinking. The structure formed by the thermal-initiated self-crosslinking has higher thermal stability, and the phenylethynyl serving as an active group of the thermal-initiated self-crosslinking has the characteristics of no release of byproducts, no need of catalysts and the like during crosslinking, so that the structure is widely researched by students.
A patent of invention containing phenylethynyl dianhydride monomer and its synthesis and application (CN104478838A) was filed in 2014 by Guangxi Yaohong et al, and SCI articles published in 2017, such as "Micropole polyimides networks structured through a two-step polymerization approach", and "carbon dioxide adsorption performance" (Polymer, chem.,2017,8, 1298-one 1305) and "From a flexible polyimide to a Microporous polyimide adsorption" (Polymer,2017,115: 176-183); however, the polymer synthesized by the method has the problems that the cross-linked side chain is lengthened due to the fact that the phenylethynyl group introduced into the dianhydride monomer is on the biphenyl group, and further the aperture of the synthesized polymer is large, and gas adsorption is not facilitated.
Disclosure of Invention
In order to solve the problems, the invention designs and synthesizes the crosslinkable hyperbranched polyimide, which utilizes the characteristics that phenylethynyl has thermal-induced crosslinking, does not generate byproducts, does not need catalysts, has high rigidity after crosslinking and the like, introduces the phenylethynyl into a polymer system, simultaneously shortens the length of a crosslinking side chain, obtains the crosslinked polyimide material through thermal crosslinking treatment, improves the thermal property and the mechanical property of the polymer, generates a network structure, has the characteristics of small pore size distribution, larger micropore volume and better gas adsorption effect compared with the prior art, and further expands the application of the crosslinked polyimide in the field of gas adsorption materials.
The cross-linkable hyperbranched polyimide has a structural formula shown in the specification when being terminated by anhydride
When blocked by amino, the structural formula is
Any one of them.
The preparation steps of the crosslinkable hyperbranched polyimide are as follows:
A. the dianhydride monomer is prepared by the following synthetic route:
step 1): mixing a mixture of 1: (2-2.4) putting 2-bromo-1, 4-hydroquinone and 4-nitrophthalonitrile into a three-necked bottle, salifying the 2-bromo-1, 4-hydroquinone with cesium carbonate of which the molar amount is 2-2.4 times of that of the hydroquinone, reacting with the 4-nitrophthalonitrile in a reaction solvent at room temperature for 12-48 hours, wherein the reaction solid content is about 20% -40%, discharging after the reaction is finished, putting into deionized water, washing for 3-4 times until the filtrate is clear, drying the obtained solid powder, and recrystallizing with a mixed solution of acetonitrile and water to obtain a bromine-containing tetranitrile monomer;
step 2): putting the bromine-containing tetranitrile monomer of the product obtained in the step 1) and triphenylphosphine into a three-necked bottle, adding a reaction solvent, stirring at normal temperature until the solid is dissolved, and adding a mixture of the bromine-containing tetranitrile monomer and the triphenylphosphine in a molar ratio of 1: (1.2-1.5) phenylacetylene, bis (triphenylphosphine) palladium dichloride and triethylamine, raising the reaction temperature to 60 ℃, adding cuprous iodide and triethylamine, raising the reaction temperature to 80 ℃ and reacting for 8-24 hours, evaporating part of triethylamine, filtering in dilute hydrochloric acid, washing for 3-4 times with deionized water until the filtrate is clear to obtain yellow powder, and recrystallizing with acetonitrile to obtain a tetranitrile monomer with a phenylethynyl-containing side group;
step 3): putting the product obtained in the step 2) with the molar ratio of 1 (20-40) and potassium hydroxide into a three-neck flask, heating and refluxing for 12-80 hours in a mixed solvent of ethanol and water, cooling to room temperature after the reaction is finished, adding dilute hydrochloric acid to adjust the pH value to 2-3, washing the solid obtained by filtering with deionized water for 3-4 times until the filtrate is clear, and drying for 24 hours at the temperature of 80 ℃ in vacuum to obtain a hydrolysate containing tetracarboxyl;
step 4): adding the product obtained in the step 3) into a mixed solvent of acetic acid and acetic anhydride, heating and refluxing for 6-10 hours, filtering while hot, and drying the cooled solid for 24-48 hours at 100 ℃ in vacuum to obtain a final product of 4, 4- (phenylethynyl-p-phenyl) diether dianhydride monomer.
The reaction solvent in the steps 1) and 2) is N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone; in the step 2), the molar ratio of the total molar amount of triphenylphosphine, palladium bis (triphenylphosphine) dichloride and cuprous iodide to the bromine-containing tetranitrile monomer is (0.01-0.1): 1;
in the step 3), the solid content is the ratio of the mass of the reaction substance to the volume of the solvent;
in the step 2), the solvent volume ratio of N, N-dimethylformamide or N, N-dimethylacetamide to triethylamine is (1-10) to (1-10); in the step 3), the volume ratio of the mixed solvent of the ethanol and the water is 1: 1; in the step 4), the volume ratio of the mixed solvent of acetic acid and acetic anhydride is (1-3): (1-3).
B. The preparation of the hyper-branched polyimide is carried out,
b1, preparing the acid anhydride terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methylpyrrolidone to obtain a diether dianhydride solution, dropwise adding an aromatic polyamine solution dissolved in the N-methylpyrrolidone into the diether dianhydride solution, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain anhydride-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is (2-3) to 1;
b2, preparing the amino-terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methyl pyrrolidone to obtain a diether dianhydride solution, dropwise adding the diether dianhydride solution into an aromatic polyamine solution dissolved in the N-methyl pyrrolidone, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating the reaction system to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain amino-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is 1 (1-2);
wherein the aromatic polyamine is melamine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 1,3, 5-tris (4-aminophenoxy) benzene, 1,3, 5-tris (4-amino-2-trifluoromethylphenoxy) benzene, 2,4, 6-tris (4-aminophenyl) pyridine, 2,4, 6-tris- (4-aminophenoxy) -1,3, 5-triazine, tris (3-aminophenyl) triphenylphosphine oxide, 2 ', 7, 7' -tetraamino-9, 9 '-spirobifluorene, tetrakis (4-aminophenyl) methane, 4' -tetraaminophthalocyanine or 4 of copper, zinc, iron, cobalt, nickel, 4 ', 4 ", 4"' -tetraaminophthalocyanine chelate, 4-tetraaminophenyl porphyrin or 4,4 ', 4 ", 4"' -tetraaminophenyl porphyrin chelate of copper, zinc, iron, cobalt, nickel.
The cross-linked polyimide is obtained after the cross-linked polyimide is subjected to thermal cross-linking treatment, and the thermal cross-linking treatment method comprises the following steps:
and (3) transferring the hyperbranched polyimide obtained in the step B1 or B2 into a container, heating to 360 ℃ by taking diphenyl sulfone as a reaction solvent, carrying out high-temperature crosslinking reaction for 24-36 hours, cooling to 150 ℃, putting the mixture into acetone, washing the obtained solid for 48 hours by taking acetone as a solvent through a Soxhlet extractor, and drying for 36-48 hours at the temperature of 100-120 ℃ in vacuum to obtain the crosslinked hyperbranched polyimide.
The invention has the beneficial effects that:
the cross-linked hyperbranched polyimide provided by the invention has high cross-linking density and good controllability. Compared with the scheme disclosed by CN104478838A, the polymer has the characteristics of small pore size distribution, larger micropore volume and better gas adsorption effect, and further expands the application of the cross-linked polyimide in the field of gas adsorption materials.
Drawings
FIG. 1 is an infrared spectrum of 4,4, - (phenylethynyl-p-phenylene) diether dianhydride;
FIG. 2 is a hydrogen nuclear magnetic spectrum of 4,4, - (phenylethynyl-p-phenylene) diether dianhydride;
FIG. 3 is a carbon nuclear magnetic spectrum of 4,4, - (phenylethynyl-p-phenylene) diether dianhydride;
FIG. 4 is an infrared spectrum of an anhydride-terminated uncrosslinked hyperbranched polyimide and a crosslinked hyperbranched polyimide prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as a tetraamine;
FIG. 5 is a TGA curve for anhydride terminated uncrosslinked hyperbranched polyimide and crosslinked hyperbranched polyimide prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as tetramine;
FIG. 6 is a 77K nitrogen adsorption curve for anhydride-terminated uncrosslinked hyperbranched polyimide (a) and crosslinked hyperbranched polyimide (b) prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as tetramine;
FIG. 7 is a pore size distribution curve for 77K nitrogen adsorption of anhydride-terminated uncrosslinked hyperbranched polyimide and crosslinked hyperbranched polyimide prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as tetramine;
FIG. 8 is a scanning electron microscope image of anhydride-terminated uncrosslinked hyperbranched polyimide (a) and crosslinked hyperbranched polyimide (b) prepared using 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as tetramine.
Detailed Description
The technical solution of the present invention is further explained and illustrated in the form of specific examples.
Example 1: preparation of 4, 4- (phenylethynyl-p-phenyl) diether dianhydride
The preparation method of 4, 4- (phenylethynyl-p-phenyl) diether dianhydride comprises the following steps:
step (1): mixing a mixture of 1: (2-2.4) putting 2-bromo-1, 4-hydroquinone and 4-nitrophthalonitrile into a three-necked bottle, salifying the 2-bromo-1, 4-hydroquinone with cesium carbonate of which the molar amount is 2-2.4 times of that of the hydroquinone, reacting with the 4-nitrophthalonitrile in a reaction solvent at room temperature for 12-48 hours, wherein the reaction solid content is about 20% -40%, discharging after the reaction is finished, putting into deionized water, washing for 3-4 times until the filtrate is clear, drying the obtained solid powder, and recrystallizing with a mixed solution of acetonitrile and water to obtain a bromine-containing tetranitrile monomer;
step (2): putting the bromine-containing tetranitrile monomer of the product in the step (1) and triphenylphosphine into a three-necked bottle, adding a reaction solvent, stirring at normal temperature until the solid is dissolved, and adding a mixture of the bromine-containing tetranitrile monomer and the triphenylphosphine in a molar ratio of 1: (1.2-1.5) phenylacetylene, bis (triphenylphosphine) palladium dichloride and triethylamine, raising the reaction temperature to 60 ℃, adding cuprous iodide and triethylamine, raising the reaction temperature to 80 ℃ and reacting for 8-24 hours, evaporating part of triethylamine, filtering in dilute hydrochloric acid, washing for 3-4 times with deionized water until the filtrate is clear to obtain yellow powder, and recrystallizing with acetonitrile to obtain a tetranitrile monomer with a phenylethynyl-containing side group;
and (3): putting the product obtained in the step (2) and potassium hydroxide in a molar ratio of 1: 20-40 into a three-neck flask, heating and refluxing for 12-80 hours in a mixed solvent of ethanol and water, cooling to room temperature after the reaction is finished, adding dilute hydrochloric acid to adjust the pH value to 2-3, washing the filtered solid with deionized water for 3-4 times until the filtrate is clear, and drying for 24 hours at 80 ℃ in vacuum to obtain a hydrolysate containing tetracarboxyl;
and (4): and (3) adding the product obtained in the step (3) into a mixed solvent of acetic acid and acetic anhydride, heating and refluxing for 6-10 hours, filtering while the mixture is hot, and drying the cooled solid for 24-48 hours at 100 ℃ in vacuum to obtain a final product of 4, 4- (phenylethynyl-p-phenyl) diether dianhydride monomer.
The reaction solvent is N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone; in the reaction (2), the molar ratio of the total molar amount of triphenylphosphine, palladium bis (triphenylphosphine) dichloride and cuprous iodide to the bromine-containing tetranitrile monomer is (0.01-0.1): 1.
In the reaction (1), the solid content is the ratio of the mass of the reaction to the volume of the solvent.
In the reaction (2), the solvent volume ratio of N, N-dimethylformamide or N, N-dimethylacetamide to triethylamine is 1-10: 1-10; in the reaction (3), the volume ratio of the mixed solvent of the ethanol and the water is 1: 1; in the reaction (4), the volume ratio of the mixed solvent of acetic acid and acetic anhydride is (1-3): (1-3).
FIG. 1 shows the IR spectra of 4,4, - (phenylethynyl-p-phenylene) diether dianhydride at 1849 and 1788cm-1The vibration positions correspond to asymmetric and symmetric stretching vibration of 4,4, - (phenylethynyl p-phenyl) diether dianhydride carbonyl, 2212cm-1Characteristic absorption peak corresponding to carbon-carbon triple bond;
FIGS. 2 and 3 show hydrogen nuclear magnetic spectra and carbon nuclear magnetic hydrogen spectra of 4,4, - (phenylethynyl-p-phenyl) diether dianhydride, wherein the chemical shifts and integrated areas marked on the figures correspond to the structures of 4,4, - (phenylethynyl-p-phenyl) diether dianhydride, respectively, and the preparation of the 4,4, - (phenylethynyl-p-phenyl) diether dianhydride monomer is proved;
example 2: the preparation method of the acid anhydride terminated hyperbranched polyimide by taking tetra (4-aminophenyl) methane as a tetramine monomer and 4, 4- (phenylethynyl-p-phenylene) diether dianhydride as dianhydride comprises the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methyl pyrrolidone to obtain a diether dianhydride solution, dropwise adding a tetra (4-aminophenyl) methane solution dissolved in the N-methyl pyrrolidone into the diether dianhydride solution, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating the reaction system to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with the ethyl alcohol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain anhydride-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the tetra (4-aminophenyl) methane is (2-3) to 1;
and putting the obtained 4, 4- (phenylethynyl-p-phenyl) diether dianhydride terminated hyperbranched polyimide into a three-neck flask, heating diphenyl sulfone serving as a reaction solvent to 360 ℃, carrying out high-temperature crosslinking reaction for 24-36 hours, cooling to 150 ℃, putting the product into acetone, washing the obtained solid with acetone serving as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100-120 ℃ for 36-48 hours in vacuum to obtain the crosslinked hyperbranched polyimide.
The preparation routes of 4, 4- (phenylethynyl-p-phenylene) diether dianhydride terminated hyperbranched polyimide and crosslinked hyperbranched polyimide are as follows:
FIG. 4 shows the IR spectra of anhydride-terminated uncrosslinked hyperbranched polyimide and crosslinked hyperbranched polyimide prepared from 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane tetraamine, all of which do not have an IR spectrum of 1650cm-1The absorption peak of the amide carbonyl group indicates that imidization has proceeded completely; after the thermal crosslinking treatment, it was located at 2211cm-1The absorption peak of the phenylethynyl group is completely disappeared, which shows that the phenylethynyl group of the hyperbranched polyimide side chain is subjected to crosslinking reaction, and the crosslinked hyperbranched polyimide is successfully prepared.
FIG. 5 is a TGA curve of anhydride terminated uncrosslinked hyperbranched polyimide and crosslinked hyperbranched polyimide prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetrakis (4-aminophenyl) methane as tetramine, wherein the crosslinked hyperbranched polyimide shows weight loss at the initial stage (<200 ℃) after temperature rise, mainly due to the solvent and gas adsorbed in the porous network; the decomposition of the main chain of the crosslinked hyperbranched polyimide occurs after 500 ℃, and the carbon residue rate at 800 ℃ exceeds 65%, which shows that the polymer has better thermal stability after thermal crosslinking.
FIG. 6 shows that 4, 4- (phenylethynyl-p-phenyl) diether dianhydride is used as dianhydride, and tetra (4-Aminophenyl) methane as the 77K nitrogen adsorption curve of anhydride-terminated uncrosslinked hyperbranched polyimide (a) and crosslinked hyperbranched polyimide (b) prepared from tetramine, wherein the calculated BET surface area of the uncrosslinked hyperbranched polyimide is 122m2g-1Total pore volume of 0.58m3g-1Micropore volume of 0.007m3g-1(ii) a After the thermal crosslinking treatment, the crosslinked hyperbranched polyimide shows the adsorption curve of a typical microporous material, and the BET surface area of the crosslinked hyperbranched polyimide is calculated to be 342m2g-1Total pore volume of 0.15m3g-1Micropore volume of 0.10m3g-1The volume of the micropores is obviously increased, which indicates that the porous adsorption hyperbranched polyimide is successfully prepared.
FIG. 7 is a 77K nitrogen adsorption pore size distribution curve of anhydride-terminated uncrosslinked hyperbranched polyimide and crosslinked hyperbranched polyimide prepared with 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetra (4-aminophenyl) methane as tetramine, and the pore size distribution of the hyperbranched polyimide is obtained by non-local density functional theory, and the polymer has a large number of mesopores and macropores and a small number of micropores before thermal crosslinking treatment; after the thermal crosslinking treatment at 360 ℃, a large number of micropores exist in the polymer structure and the polymer structure has a narrow pore size distribution, and is mainly concentrated near 1.27 nm.
Fig. 8 is a scanning electron microscope image of an anhydride-terminated uncrosslinked hyperbranched polyimide (a) and a crosslinked hyperbranched polyimide (b) prepared by using 4,4, - (phenylethynyl-p-phenylene) diether dianhydride and tetra (4-aminophenyl) methane as tetramine, and it can be seen from the figure that (b) after thermal crosslinking treatment exhibits a structure formed by stacking more highly aggregated nano-polymer particles than (a) before treatment, and is favorable for forming a stable microporous structure, which is a main reason why the material can be used in the field of gas adsorption materials.
Example 3: the preparation method of the amino-terminated hyperbranched polyimide comprises the following steps of taking 4, 4- (phenylethynyl-p-phenyl) diether dianhydride as dianhydride and tetra (4-aminophenyl) methane as a tetramine monomer:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methyl pyrrolidone to obtain a diether dianhydride solution, dropwise adding the diether dianhydride solution into a tetra (4-aminophenyl) methane solution dissolved in the N-methyl pyrrolidone, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating the reaction system to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with the ethyl alcohol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain amino-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the tetra (4-aminophenyl) methane is 1 (1-2).
Example 4: examples 2 and 3 were repeated using melamine as the triamine monomer in place of tetrakis (4-aminophenyl) methane to prepare anhydride-terminated and amino-terminated hyperbranched polyimides.
Example 5: examples 2 and 3 were repeated using 1,3, 5-tris (4-aminophenyl) benzene as the triamine monomer in place of tetrakis (4-aminophenyl) methane to prepare anhydride-terminated and amino-terminated hyperbranched polyimides.
Example 6: the specific preparation method for preparing the anhydride-terminated hyperbranched polyimide by taking the tetraaminophenylporphyrin as the tetramine monomer comprises the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methylpyrrolidone to obtain a diether dianhydride solution, dropwise adding a tetraaminophenylporphyrin solution dissolved in the N-methylpyrrolidone into the diether dianhydride solution, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain anhydride-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the tetraaminophenyl porphyrin is (2-3) to 1;
example 7: example 6 was repeated using tris (4-aminophenyl) amine as the triamine monomer in place of tetrakis (4-aminophenyl) methane to prepare anhydride-terminated and amino-terminated hyperbranched polyimides.
Example 8: example 6 was repeated using 1,3, 5-tris (4-aminophenoxy) benzene as the triamine monomer in place of tetrakis (4-aminophenyl) methane to prepare anhydride-terminated and amino-terminated hyperbranched polyimides.
Claims (5)
1. A crosslinkable hyperbranched polyimide, characterized in that,
when end-capped with anhydride, the structural formula is
Or
When blocked by amino, the structural formula is
Or
Any one of them.
2. The preparation method of the crosslinkable hyperbranched polyimide according to claim 1, comprising the following steps:
A. the dianhydride monomer is prepared by the following steps of,
step 1): mixing a mixture of 1: (2-2.4) putting 2-bromo-1, 4-hydroquinone and 4-nitrophthalonitrile into a three-necked bottle, salifying the 2-bromo-1, 4-hydroquinone with cesium carbonate of which the molar amount is 2-2.4 times of that of the hydroquinone, reacting with the 4-nitrophthalonitrile in a reaction solvent at room temperature for 12-48 hours, wherein the reaction solid content is 20% -40%, discharging after the reaction is finished, putting into deionized water, washing for 3-4 times until the filtrate is clear, drying the obtained solid powder, and recrystallizing with a mixed solution of acetonitrile and water to obtain a bromine-containing tetranitrile monomer;
step 2): putting the bromine-containing tetranitrile monomer of the product obtained in the step 1) and triphenylphosphine into a three-necked bottle, adding a reaction solvent, stirring at normal temperature until solid is dissolved, and adding phenylacetylene, bis-triphenylphosphine palladium dichloride and triethylamine, wherein the molar ratio of the phenylacetylene to the reactants is (1.2-1.5): 1, raising the reaction temperature to 60 ℃, adding cuprous iodide and triethylamine, raising the reaction temperature to 80 ℃, reacting for 8-24 hours, evaporating part of triethylamine, discharging in dilute hydrochloric acid, filtering, washing for 3-4 times with deionized water until the filtrate is clear, obtaining yellow powder, and recrystallizing with acetonitrile to obtain a tetranitrile monomer with a phenylethynyl-containing side group;
step 3): putting the product obtained in the step 2) with the molar ratio of 1 (20-40) and potassium hydroxide into a three-neck flask, heating and refluxing for 12-80 hours in a mixed solvent of ethanol and water, cooling to room temperature after the reaction is finished, adding dilute hydrochloric acid to adjust the pH value to 2-3, washing the solid obtained by filtering with deionized water for 3-4 times until the filtrate is clear, and drying for 24 hours at the temperature of 80 ℃ in vacuum to obtain a hydrolysate containing tetracarboxyl;
step 4): adding the product obtained in the step 3) into a mixed solvent of acetic acid and acetic anhydride, heating and refluxing for 6-10 hours, filtering while hot, and drying the cooled solid for 24-48 hours at 100 ℃ in vacuum to obtain a final product, namely 4, 4' - (phenylethynyl-p-phenyl) diether dianhydride monomer;
the reaction solvent in the steps 1) and 2) is N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone; in the step 2), the molar ratio of the total molar amount of triphenylphosphine, palladium bis (triphenylphosphine) dichloride and cuprous iodide to the bromine-containing tetranitrile monomer is (0.01-0.1): 1;
in the step 3), the solid content is the ratio of the mass of the reaction to the volume of the solvent;
in the step 2), the volume ratio of N, N-dimethylformamide or N, N-dimethylacetamide to triethylamine is (1-10) to (1-10); in the step 3), the volume ratio of the ethanol to the water is 1: 1; in the step 4), the volume ratio of the acetic acid to the acetic anhydride is (1-3): (1-3);
B. the preparation of the cross-linkable hyperbranched polyimide,
b1, preparing the acid anhydride terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methylpyrrolidone to obtain a diether dianhydride solution, dropwise adding an aromatic polyamine solution dissolved in the N-methylpyrrolidone into the diether dianhydride solution, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain anhydride-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is 2-3: 1;
b2, preparing the amino-terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methyl pyrrolidone to obtain a diether dianhydride solution, dropwise adding the diether dianhydride solution into an aromatic polyamine solution dissolved in the N-methyl pyrrolidone, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating the reaction system to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain amino-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is 1: 1-2;
wherein the aromatic polyamine is melamine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 1,3, 5-tris (4-aminophenoxy) benzene, 1,3, 5-tris (4-amino-2-trifluoromethylphenoxy) benzene, 2,4, 6-tris (4-aminophenyl) pyridine, 2,4, 6-tris- (4-aminophenoxy) -1,3, 5-triazine, tris (3-aminophenyl) triphenylphosphine oxide, 2 ', 7,7 ' -tetraamino-9, 9 ' -spirobifluorene, tetrakis (4-aminophenyl) methane, 4 ' -tetraaminophthalocyanine or 4,4 '/of copper, zinc, iron, cobalt, nickel, 4 ', 4 ' -tetraaminophthalocyanine chelate, 4-tetraaminophenyl porphyrin or 4,4 ' -tetraaminophenyl porphyrin chelate of copper, zinc, iron, cobalt, nickel.
3. A crosslinked hyperbranched polyimide, wherein the crosslinked hyperbranched polyimide is the crosslinkable hyperbranched polyimide of claim 1 crosslinked at an alkynyl position to form a crosslinked structure.
4. The cross-linked hyperbranched polyimide according to claim 3, which comprises the following specific steps:
A. the dianhydride monomer is prepared by the following steps of,
step 1): mixing a mixture of 1: (2-2.4) putting 2-bromo-1, 4-hydroquinone and 4-nitrophthalonitrile into a three-necked bottle, salifying the 2-bromo-1, 4-hydroquinone with cesium carbonate of which the molar amount is 2-2.4 times of that of the hydroquinone, reacting with the 4-nitrophthalonitrile in a reaction solvent at room temperature for 12-48 hours, wherein the reaction solid content is 20% -40%, discharging after the reaction is finished, putting into deionized water, washing for 3-4 times until the filtrate is clear, drying the obtained solid powder, and recrystallizing with a mixed solution of acetonitrile and water to obtain a bromine-containing tetranitrile monomer;
step 2): putting the bromine-containing tetranitrile monomer of the product obtained in the step 1) and triphenylphosphine into a three-necked bottle, adding a reaction solvent, stirring at normal temperature until solid is dissolved, and adding phenylacetylene, bis-triphenylphosphine palladium dichloride and triethylamine, wherein the molar ratio of the phenylacetylene to the reactants is (1.2-1.5): 1, raising the reaction temperature to 60 ℃, adding cuprous iodide and triethylamine, raising the reaction temperature to 80 ℃, reacting for 8-24 hours, evaporating part of triethylamine, discharging in dilute hydrochloric acid, filtering, washing for 3-4 times with deionized water until the filtrate is clear, obtaining yellow powder, and recrystallizing with acetonitrile to obtain a tetranitrile monomer with a phenylethynyl-containing side group;
step 3): putting the product obtained in the step 2) with the molar ratio of 1 (20-40) and potassium hydroxide into a three-neck flask, heating and refluxing for 12-80 hours in a mixed solvent of ethanol and water, cooling to room temperature after the reaction is finished, adding dilute hydrochloric acid to adjust the pH value to 2-3, washing the solid obtained by filtering with deionized water for 3-4 times until the filtrate is clear, and drying for 24 hours at the temperature of 80 ℃ in vacuum to obtain a hydrolysate containing tetracarboxyl;
step 4): adding the product obtained in the step 3) into a mixed solvent of acetic acid and acetic anhydride, heating and refluxing for 6-10 hours, filtering while hot, and drying the cooled solid for 24-48 hours at 100 ℃ in vacuum to obtain a final product, namely 4, 4' - (phenylethynyl-p-phenyl) diether dianhydride monomer;
the reaction solvent in the steps 1) and 2) is N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone; in the step 2), the molar ratio of the total molar amount of triphenylphosphine, palladium bis (triphenylphosphine) dichloride and cuprous iodide to the bromine-containing tetranitrile monomer is (0.01-0.1): 1;
in the step 3), the solid content is the ratio of the mass of the reaction substance to the volume of the solvent;
in the step 2), the solvent volume ratio of N, N-dimethylformamide or N, N-dimethylacetamide to triethylamine is (1-10) to (1-10); in the step 3), the volume ratio of the ethanol to the water is 1: 1; in the step 4), the volume ratio of the acetic acid to the acetic anhydride is (1-3): (1-3);
B. the preparation of the cross-linkable hyperbranched polyimide,
b1, preparing the acid anhydride terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methylpyrrolidone to obtain a diether dianhydride solution, dropwise adding an aromatic polyamine solution dissolved in the N-methylpyrrolidone into the diether dianhydride solution, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain anhydride-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is 2-3: 1;
b2, preparing the amino-terminated hyperbranched polyimide by the following steps:
dissolving a diether dianhydride monomer with a phenylethynyl-containing side group in N-methyl pyrrolidone to obtain a diether dianhydride solution, dropwise adding the diether dianhydride solution into an aromatic polyamine solution dissolved in the N-methyl pyrrolidone, reacting at room temperature for 8-16 hours, adding a catalytic amount of isoquinoline into a reaction system, heating to 120 ℃ for reaction for 5-6 hours, heating the reaction system to 180 ℃ for reaction for 16-24 hours, cooling, discharging, filtering in absolute ethyl alcohol, washing with ethanol as a solvent for 48 hours by using a Soxhlet extractor, and drying at 100 ℃ in vacuum for 48-60 hours to obtain amino-terminated hyperbranched polyimide; wherein the molar ratio of the diether dianhydride monomer with the phenylethynyl-containing side group to the aromatic polyamine is 1 (1-2);
wherein the aromatic polyamine is melamine, tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 1,3, 5-tris (4-aminophenoxy) benzene, 1,3, 5-tris (4-amino-2-trifluoromethylphenoxy) benzene, 2,4, 6-tris (4-aminophenyl) pyridine, 2,4, 6-tris- (4-aminophenoxy) -1,3, 5-triazine, tris (3-aminophenyl) triphenylphosphine oxide, 2 ', 7,7 ' -tetraamino-9, 9 ' -spirobifluorene, tetrakis (4-aminophenyl) methane, 4 ' -tetraaminophthalocyanine or 4,4 '/of copper, zinc, iron, cobalt, nickel, 4 ", 4" ' -tetraaminophthalocyanine chelate, 4-tetraaminophenyl porphyrin or 4,4 ', 4 ", 4" ' -tetraaminophenyl porphyrin chelate of copper, zinc, iron, cobalt, nickel;
C. thermal crosslinking treatment
And (3) transferring the hyperbranched polyimide obtained in the step B1 or B2 into a container, heating to 360 ℃ by taking diphenyl sulfone as a reaction solvent, carrying out high-temperature crosslinking reaction for 24-36 hours, cooling to 150 ℃, putting the mixture into acetone, washing the obtained solid for 48 hours by taking acetone as a solvent through a Soxhlet extractor, and drying for 36-48 hours at the temperature of 100-120 ℃ in vacuum to obtain the crosslinked hyperbranched polyimide.
5. Use of the cross-linked hyperbranched polyimide according to claim 3 as a porous material in the field of gas adsorption.
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