Hyperbranched polyimide containing phenanthrene ring structure and preparation method and application thereof
Technical Field
The invention relates to the field of material science, in particular to hyperbranched polyimide containing a phenanthrene ring structure and a preparation method thereof.
Technical Field
Polyimide is a high molecular material with excellent heat resistance, and has very wide application in various fields of aviation, aerospace, electrical, machinery, chemical engineering, microelectronics and the like due to excellent comprehensive performance. However, the polyimide has strong interaction between molecular chains, so that the polyimide has insoluble and infusible characteristics. The hyperbranched polymer has the unique advantages of low viscosity, a large number of terminal functional groups and the like. The introduction of hyperbranched structures into polyimide polymer chains to synthesize soluble hyperbranched polyimides (HBPIs) is one of the important means for improving the processability of polyimides.
Hyperbranched polyimides (HBPIs) have a series of unique physical and chemical properties such as good solubility, no chain entanglement, difficulty or no crystallization, low solution and melt viscosity, excellent heat resistance, solvent resistance, high dielectric properties and the like due to the combination of the advantages of hyperbranched polymers and polyimides, and are attracted by the majority of researchers in recent years. At present, hyperbranched polyimide is mainly applied to membrane materials such as gas separation membranes, permeable membranes and the like, and other high and new technical fields such as optical waveguides, photosensitivity, liquid crystals, dielectric materials, sensors (detection electrodes) and the like.
Phenanthrene rings are important compounds of polycyclic aromatic hydrocarbons and have a large-volume rigid conjugated structure. According to the invention, the phenanthrene ring is introduced into the main chain of the hyperbranched polyimide, so that on one hand, the thermal performance of the polymer can be improved, on the other hand, due to the introduction of the phenanthrene ring with large volume, the molecular chain spacing of the hyperbranched polyimide is enlarged, and the free volume of the polymer is increased, thereby further improving the solubility and the processability of the polymer and improving the gas permeability of the polymer. The hyperbranched polyimide containing the phenanthrene ring structure has excellent heat resistance and solubility, and has good application prospects in the fields of high temperature resistance, light sensitivity, optical waveguide, gas permeation separation membranes and other materials.
Disclosure of Invention
The invention aims to provide hyperbranched polyimide containing a phenanthrene ring structure.
The invention also aims to provide a preparation method of the phenanthrene ring structure-containing hyperbranched polyimide.
The purpose of the invention is realized as follows: a hyperbranched polyimide material containing a phenanthrene ring structure has a molecular structure general formula as follows:
wherein: m, z and n are 1-10000, and the structure of Y is shown as a general formula I:
wherein Ar is1Selected from any one of the following structural formulas:
preferably, Ar is
1Is selected from
Wherein Ar is2And Ar3Selected from any one of the following structural formulas:
preferably, Ar is
2Is composed of
One of (1);
preferably, Ar is
3Is composed of
One kind of (1).
X is selected from one or more than one of the following structural formulas:
preferably, m, z and n are integers of 100-5000.
Further, m, z and n are preferably integers of 1000 to 2000.
The invention also aims to provide a preparation method of the phenanthrene ring structure-containing hyperbranched polyimide, which comprises the following steps: dissolving triamine containing a Y structure and dianhydride containing an X structure in a molar ratio of 1 (0.8-2.5) in one or more mixed strong polar aprotic organic solvents selected from N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1, 4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol and tetrahydrofuran in an argon atmosphere, wherein the total mass of the diamine containing the Y structure and the dianhydride containing the X structure accounts for 0.5-30% of the total mass of the reaction materials, stirring and reacting at-10-55 ℃ for 0.5-90 h to obtain a homogeneous hyperbranched polyamide acid solution, and dehydrating the hyperbranched polyamide acid solution through thermal imidization or chemical imidization to obtain the hyperbranched polyimide material.
The thermal imidization method comprises the following specific operation steps: and (2) coating the hyperbranched polyamic acid glue solution on a glass plate in a blade mode, then placing the glass plate in a vacuum oven, vacuumizing, and heating up according to the following temperature program: and (3) heating the room temperature to 80-120 ℃, keeping the temperature for 0.8-3 h, heating the room temperature to 150-200 ℃, keeping the temperature for 0.8-2 h, heating the room temperature to 300-400 ℃, keeping the temperature for 0.8-2 h, and cooling the room temperature to obtain the hyperbranched polyimide film or powder.
The chemical imidization method comprises the following specific operation steps: adding pyridine/acetic anhydride, triethylamine/acetic anhydride or sodium acetate/acetic anhydride as dehydrating agent into the hyperbranched polyamic acid solution, heating and stirring, heating to 40-170 ℃, continuing stirring for 4-24 h, cooling to room temperature, then pouring into methanol or ethanol to obtain hyperbranched polyimide precipitate, filtering, washing and drying, to obtain hyperbranched polyimide powder, if membrane material preparation is needed, the polyimide powder can be dissolved in N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-dimethyl acetamide (DMAc), N-dimethyl formamide (DMF), m-Cresol (m-Cresol) or Tetrahydrofuran (THF), heating to completely dissolve, coating the polyimide solution on a glass plate in a scraping way, drying at 70-200 ℃ in vacuum to remove the solvent, and cooling to obtain the polyimide film.
The preparation method of the phenanthrene ring structure-containing hyperbranched polyimide provided by the invention is simple and diverse in preparation process and low in condition requirement, so that the preparation method is suitable for industrial production. According to the invention, the phenanthrene ring is introduced into the main chain of the hyperbranched polyimide, so that on one hand, the thermal performance of the polymer can be improved, on the other hand, due to the introduction of the phenanthrene ring with large volume, the molecular chain spacing of the hyperbranched polyimide is enlarged, and the free volume of the polymer is increased, thereby further improving the solubility and the processability of the polymer and improving the gas permeability of the polymer. The hyperbranched polyimide containing the phenanthrene ring structure has excellent heat resistance and solubility, and has good application prospects in the fields of high temperature resistance, light sensitivity, optical waveguide, gas permeation separation membranes and other materials.
Drawings
FIG. 1 is an infrared spectrum of the hyperbranched polyimides of examples 1 to 6, wherein:
a corresponds to example 1
b corresponds to example 4
c corresponds to example 3
d corresponds to example 5
e corresponds to example 2
f for example 6
From the infrared spectrum, at 1776 and 1722cm-1Around the imine ring is asymmetric and symmetric stretching vibration of carbonyl group at 1370cm-1An obvious C-N bond stretching vibration characteristic absorption peak is generated at 1079-796 cm-1The nearby absorption peaks are the deformation vibration absorption peaks of Ar-H, which all show that the synthesis of examples 1-6 has been successful.
Detailed Description
The following examples are given to illustrate the invention in more detail, it being noted that the following examples are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the above disclosure, may make insubstantial modifications and adaptations of the invention while remaining within the scope of the invention.
Example 1
0.4362g (2mmol) of pyromellitic dianhydride (PMDA) and 36ml of N, N-dimethylformamide are added into a three-neck flask, argon is introduced, the temperature is raised to 30 ℃, and triamine monomer N is added2-(6-aminonaphthalen-2-yl)-N2Dissolving 0.6168g (1mmol) of- (10- (6-aminonaphthalene-2-yl) phenanthren-2-yl) naphthalene-2,6-diamine into 40ml of N, N-dimethylformamide, uniformly dripping the N, N-dimethylformamide into a three-neck flask by using a constant pressure dropping funnel for 1-2 h, continuing to react for 14h, then adding 6ml of acetic anhydride and 2ml of triethylamine, heating to 45 ℃ for continuing to react for 12h, cooling to room temperature after the reaction is finished, discharging into ethanol, filtering, washing, repeating for 2-3 times, and finally placing at 80 ℃ for vacuum dryingDrying in a drying oven for 24 hours to obtain the dark reddish brown hyperbranched polyimide polymer, which has the following structural formula:
example 2
0.4515g (2.07mmol) of pyromellitic dianhydride (PMDA) and 15ml of N, N-dimethylacetamide are added into a three-neck flask, argon is introduced, the temperature is raised to 30 ℃, and triamine monomer N is added1-(4-aminophenyl)-N1Dissolving 0.4666g (1mmol) of- (1- (4-aminophenyl) phenanthren-4-yl) bezene-1, 4-diamine in 15ml of N, N-dimethylacetamide, uniformly dripping the mixture into a three-neck flask for 1-2 h by using a constant pressure dropping funnel, continuing to react for 16h, adding 6.2ml of acetic anhydride and 2.1ml of triethylamine, heating to 45 ℃ for continuing to react for 15h, cooling to room temperature after the reaction is finished, discharging into methanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at 80 ℃ for 24h to obtain a yellow hyperbranched polyimide polymer, wherein the structural formula of the hyperbranched polyimide polymer is as follows:
example 3
Adding 0.4413g (1.5mmol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) and 10ml of N-methylpyrrolidone into a three-neck flask, introducing argon, heating to 30 ℃, dissolving 7,7' - ((3- (7-amino-9-oxo-9H-fluoro-2-yl) phenylanthren-9-yl) azanediyl) bis (2-amino-9H-fluoro-9-one) 0.7729g (1mmol) of triamine monomer into 8ml of N-methylpyrrolidone, uniformly dripping the N-methylpyrrolidone into the three-neck flask by using a constant pressure dropping funnel for 1-2H, continuing to react for 24H, then adding 12ml of acetic anhydride and 3ml of triethylamine, heating to 45 ℃, continuing to react for 15H, discharging the mixture after the reaction is finished and cooled to room temperature, discharging the mixture into ethanol, filtering, washing, repeating for 2-3 times, finally, the obtained product is placed in a vacuum drying oven at 80 ℃ for drying for 24 hours to obtain a brown hyperbranched polyimide polymer, the structural formula of which is as follows:
example 4
N1-(4-aminophenyl)-N1Adding 0.9332g (2mmol) of- (10- (4-aminophenyl) phenanthren-9-yl) bezene-1, 4-diamineand 8ml of N, N-dimethylformamide into a three-neck flask, introducing argon, heating to 30 ℃, dissolving 0.6444g (2mmol) of 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) into 8ml of N, N-dimethylformamide, uniformly dropping the solution into the three-neck flask for 1-2 h by using a constant pressure dropping funnel, continuously reacting for 15h, adding 6ml of acetic anhydride and 2ml of triethylamine, heating to 45 ℃, continuously reacting for 10h, cooling to room temperature after the reaction is finished, discharging the product into ethanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at 80 ℃ for 24h to obtain a tan hyperbranched polyimide polymer, wherein the structural formula of the hyperbranched polyimide polymer is as follows:
example 5
N2-(5-aminothiophen-2-yl)-N2Adding 0.9693g (2mmol) of (9- (5-aminothiophen-2-yl) phenanthren-3-yl) thiophene-2, 5-d-iamine and 5ml of N, N-dimethylacetamide into a three-neck flask, introducing argon, heating to 30 ℃, dissolving 0.8618g (1.94mmol) of hexafluorodianhydride (6FDA) into 5.5ml of N, N-dimethylacetamide, uniformly dropping the solution into the three-neck flask by using a constant pressure dropping funnel for 1-2 h, continuously reacting for 15h, adding 6ml of acetic anhydride and 2ml of triethylamine, heating to 45 ℃ for continuously reacting for 12h, cooling to room temperature after the reaction is finished, discharging the solution into methanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at 80 ℃ for 24h to obtain a reddish brown hyperbranched polyimide polymer, wherein the structural formula is as follows:
example 6
N1-(4-aminophenyl)-N1- (8- (4-aminophenyl) phenanthren-1-yl) bezene-1, 4-diamine0.9332g (2mmol) and 3ml of N, N-dimethylformamide were charged into a three-necked flask, argon gas was introduced, the temperature was raised to 30 ℃, 0.3256g (1.66mmol) of cyclobutanetetracarboxylic dianhydride (CBDA) was dissolved in 2ml of N, N-dimethylformamide, and the resulting solution was uniformly dropped into the three-necked flask with a constant pressure dropping funnel for 1 to 2 hours, followed by further reaction for 20 hours. Scraping the obtained hyperbranched polyimide acid glue solution on a dry and clean glass plate, then placing the glass plate in a vacuum oven, vacuumizing, drying for 3h under 80 ℃, then heating to 120 ℃, then keeping the temperature for the whole process for 2h, heating from 120 ℃ to 200 ℃, then keeping the temperature for the whole process for 2h, heating from 200 ℃ to 350 ℃, keeping the temperature for the whole process for 1.5h, cooling and taking out the hyperbranched polyimide film, wherein the structural formula of the hyperbranched polyimide film is as follows:
the hyperbranched polyimides prepared in examples 1 to 6 were each subjected to a glass transition temperature (T) using a differential scanning calorimeter (DSC204) of Chiz corporation and a thermogravimetric analyzer (Q50) of TA corporationg) And 5% thermogravimetric temperature (T5%) as shown in Table 1, and solubility data of hyperbranched polyimide as shown in Table 2.
TABLE 1 thermal Properties of hyperbranched polyimides
TABLE 2 solubility of hyperbranched polyimides
Note: + represents complete dissolution at room temperature
As can be seen from tables 1 and 2, the hyperbranched polyimide containing a phenanthrene ring structure of the present invention has high glass transition temperature and thermal stability, and excellent solubility.