CN108997578B - High-heat-resistance hyperbranched polyimide and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a high heat-resistant hyperbranched polyimide, and a preparation method and application thereof. The hyperbranched polyimide material is prepared from aromatic triamine and various tetracarboxylic acid dianhydrides serving as raw materials through imidization. The hyperbranched polyimide has higher glass transition temperature and thermal stability, lower thermal expansion coefficient and excellent solubility. The synthesis method of the invention has simple and various processes, thus being suitable for industrial production. The hyperbranched polyimide disclosed by the invention has a good application prospect in the high-temperature resistant field and the material field of gas permeation separation membranes and the like.
Description
Technical Field
The invention relates to the field of material science, in particular to high-heat-resistance hyperbranched polyimide and a preparation method and application thereof.
Technical Field
Polyimide refers to a class of polymers that contain an imide ring in the main chain. They are classified into aromatic polyimides and aliphatic polyimides according to their molecular structures. Among them, aromatic polyimide is easy to prepare, especially high in thermal stability due to its low dielectric property, high mechanical property; but its solubility and processability are poor.
In recent years, researchers have introduced branched structures into polyimides to prepare hyperbranched polyimides (HBPIs) in order to improve the solubility and processability of aromatic polyimides. Hyperbranched polyimides have the advantages of both polyimides and hyperbranched polymers and have a series of excellent comprehensive properties, such as high temperature resistance, high strength, high dielectric, low or no crystallinity, low solution viscosity, good solubility, and the like. The product is developed and applied to the fields of high and new technology materials such as photosensitivity, optical waveguide, liquid crystal, sensors (detection electrodes) and dielectric materials.
Compared with linear polyimide materials, hyperbranched polyimide has large distance between molecular chains, so that the solubility of the hyperbranched polyimide is improved, but the heat resistance of the hyperbranched polyimide is relatively reduced, so that the hyperbranched polyimide has limited wide application in the fields of aerospace and aviation aircraft structures or functional parts, and parts of rockets, missiles and the like. Therefore, on the basis of keeping the high solubility of the hyperbranched polyimide, the heat resistance of the hyperbranched polyimide is improved, which has important significance for expanding the application of the hyperbranched polyimide in the high temperature resistant field.
The hyperbranched polyimide main chain contains a plurality of rigid aromatic structures, so that the heat resistance of the polymer can be improved, and the distance between polymer chains can be enlarged, the free volume of the polymer can be increased, the solubility and the processability of the polymer can be further improved, and the gas permeability of the polymer can be improved. The hyperbranched polyimide disclosed by the invention has high glass transition temperature and thermal stability, a lower thermal expansion coefficient and excellent solubility, and has a better application prospect in the fields of high temperature resistance and materials such as gas permeation separation membranes.
Disclosure of Invention
The invention aims to provide highly heat-resistant hyperbranched polyimide.
The invention also aims to provide a preparation method of the high heat-resistant hyperbranched polyimide.
The purpose of the invention is realized as follows: a highly heat-resistant hyperbranched polyimide material has a molecular structural 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 is1Any one selected from the following structural formulas：
Wherein Ar is2And Ar3Selected from any one of the following structural formulas:
preferably, Ar is2Is selected from
One of (1);
preferably, Ar is3Is selected from
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 high heat-resistant 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 high heat-resistant hyperbranched polyimide provided by the invention has simple and various preparation processes and low requirement on conditions, thereby being suitable for industrial production. The hyperbranched polyimide main chain contains a plurality of rigid aromatic structures, so that the heat resistance of the polymer can be improved, and the distance between polymer chains can be enlarged, the free volume of the polymer can be increased, the solubility and the processability of the polymer can be further improved, and the gas permeability of the polymer can be improved. The hyperbranched polyimide disclosed by the invention has high glass transition temperature and thermal stability, a lower thermal expansion coefficient and excellent solubility, and has a better application prospect in the fields of high temperature resistance and materials such as gas permeation separation membranes.
Drawings
FIG. 1 is an infrared spectrum of the hyperbranched polyimides of examples 1 to 5, 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
From the infrared spectrum, at 1776 and 1722cm-1Around the asymmetric and symmetric stretching vibration of the carbonyl group on the imine ring at 1355cm-1Has an obvious C-N bond stretching vibration characteristic absorption peak of 1080-800 cm-1The nearby absorption peaks are the deformation vibration absorption peaks of Ar-H, which all show that the synthesis of examples 1-5 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 added4,N4-bis(4-aminophenyl)-[1,1'-biphenyl]Dissolving 0.3665g (1mmol) of-4, 4' -diamine into 40ml of N, N-dimethylformamide, uniformly dropping the N, N-dimethylformamide into a three-neck flask by using a constant-pressure dropping funnel for 1-2 h, then continuing to react for 12h, then adding 6ml of acetic anhydride and 2ml of triethylamine, heating to 45 ℃, continuing to react for 10h, 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 2
0.903g (4.14mmol) of pyromellitic dianhydride (PMDA) and 3ml of N, N-dimethylacetamide are added into a three-neck flask, argon is introduced, the temperature is raised to 30 ℃, and a triamine monomer N is added3,N3-bis(4-aminophenyl)-[1,1'-biphenyl]Uniformly dropping 0.733g (2mmol) of-3, 4' -diamine into 2ml of N, N-dimethylacetamide by using a constant-pressure dropping funnel for 1-2 h, then continuously reacting for 15h, then adding 12.4ml of acetic anhydride and 4.2ml of triethylamine, heating to 45 ℃ for continuously reacting for 12h, cooling to room temperature after the reaction is finished, discharging in ethanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at 80 ℃ for 24h to obtain a brown hyperbranched polyimide polymer, wherein the structural formula of the hyperbranched polyimide polymer is as follows:
example 3
0.4413g (1.5mmol) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA) and 10ml of N-methylpyrrolidone are added into a three-neck flask, argon is introduced, the temperature is raised to 30 ℃, and a triamine monomer N is added2,N2-bis(4-aminophenyl)-[1,1'-biphenyl]Dissolving 0.3665g (1mmol) of-2, 4' -diamine in 8ml of N-methylpyrrolidone, uniformly dropping the N-methylpyrrolidone into a three-neck flask by using a constant pressure dropping funnel for 1-2 h, continuing to react for 24h, adding 12ml of acetic anhydride and 3ml of triethylamine, heating to 4%Continuing to react for 10 hours at the temperature of 5 ℃, cooling to room temperature after the reaction is finished, discharging in methanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at the temperature of 80 ℃ for 24 hours to obtain the brown hyperbranched polyimide polymer, wherein the structural formula of the hyperbranched polyimide polymer is as follows:
example 4
N2-(6-aminonaphthalen-2-yl)-N2- (4- (5-aminophenyl-2-yl) phenyl) naphthalene-2,6-diamin e 0.9452g (2mmol) and 8ml of N, N-dimethylformamide were put in a three-necked flask, introducing argon, heating to 30 ℃, dissolving 0.6444g (2mmol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) in 8ml of N, N-dimethylformamide, uniformly dropping into a three-neck flask by using a constant pressure dropping funnel for 1-2 h, then continuously reacting for 14h, then 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 in ethanol, filtering, washing, repeating for 2-3 times, and finally drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain a tawny hyperbranched polyimide polymer, wherein the structural formula of the tawny hyperbranched polyimide polymer is as follows:
example 5
N2-(4-(6-aminonaphthalen-2-yl)phenyl)-N2- (5-aminothiophen-2-yl) thiophene-2,5-diamine0.8571g (2mmol) and 5ml of N, N-dimethylacetamide are added into a three-neck flask, argon is introduced, the temperature is raised to 30 ℃, 0.8618g (1.94mmol) of hexafluorodianhydride (6FDA) is dissolved into 5.5ml of N, N-dimethylacetamide and is uniformly dripped into the three-neck flask by a constant pressure dropping funnel for 1-2 h, then the reaction is continued for 14h, 6ml of acetic anhydride and 2ml of triethylamine are added, the temperature is raised to 50 ℃ for further reaction for 12h, after the reaction is finished and cooled to the room temperature, the materials are discharged into methanol, filtered and washed, repeated for 2-3 times, and finally the mixture is dried in a vacuum drying oven at 80 ℃ for 24h to obtain the reddish brown hyperbranched polyimide poly (arylene-co-imide)A compound having the formula:
the hyperbranched polyimides prepared in examples 1 to 5 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
+ represents complete dissolution at room temperature
As can be seen from tables 1 and 2, the hyperbranched polyimides of the present invention have high glass transition temperature and thermal stability, and excellent solubility.
Claims (9)
1. A highly heat-resistant hyperbranched polyimide material has a molecular structural general formula as follows:
wherein: m, z and n are 1-10000, and the structure of Y is shown as a general formula I:
I：
wherein Ar is1Selected from the following knotsAny one of the formulae:
x is selected from one or more than one of the following structural formulas:
ar in the structural formula I2And Ar3Selected from any one of the following structural formulas:
2. the highly heat-resistant hyperbranched polyimide material as claimed in claim 1, wherein: the hyperbranched polyimide material is prepared into powder or film.
3. The highly heat-resistant hyperbranched polyimide material as claimed in claim 1, wherein: the preparation method comprises the following steps: dissolving triamine containing a Y structure and dianhydride containing an X structure in a strong-polarity aprotic organic solvent according to a molar ratio of 1: 0.8-1: 2.5 in an argon atmosphere, stirring and reacting at-10-55 ℃ for 0.5-90 h to obtain a homogeneous transparent hyperbranched polyamic acid solution, and imidizing the hyperbranched polyamic acid solution to obtain the hyperbranched polyimide material.
4. The highly heat-resistant hyperbranched polyimide material as claimed in claim 3, wherein: the total mass of the triamine containing the Y structure and the dianhydride containing the X structure accounts for 0.5-30% of the total mass of the reaction materials.
5. The highly heat-resistant hyperbranched polyimide material as claimed in claim 3, wherein: the strong polar aprotic organic solvent is one or more of N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1, 4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol and tetrahydrofuran.
6. The highly heat-resistant hyperbranched polyimide material as claimed in claim 3, wherein: the method for obtaining polyimide by imidizing the hyperbranched polyamic acid solution is thermal imidization or chemical imidization.
7. The highly heat-resistant hyperbranched polyimide material as claimed in claim 6, wherein: the specific operation of thermal imidization is: and (2) coating the hyperbranched polyamic acid solution glue solution on a glass plate by scraping, then placing the glass plate in a vacuum oven, vacuumizing, and heating up: 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, cooling and taking out the hyperbranched polyimide material.
8. The highly heat-resistant hyperbranched polyimide material as claimed in claim 6, wherein: the specific operation of chemical imidization is as follows: adding pyridine/acetic anhydride, triethylamine/acetic anhydride or sodium acetate/acetic anhydride as a dehydrating agent into the hyperbranched polyamic acid solution, heating and stirring, heating to 40-170 ℃, continuously stirring for 4-24 h, cooling to room temperature, pouring into methanol or ethanol to obtain hyperbranched polyimide precipitate, filtering, washing and drying to obtain hyperbranched polyimide powder, dissolving the hyperbranched polyimide powder in N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylacetamide, N-dimethylformamide, m-cresol or tetrahydrofuran, heating until the hyperbranched polyimide powder is completely dissolved, blade-coating the polyimide solution on a glass plate, vacuum-drying at 70-200 ℃ to remove the solvent, cooling and taking out the hyperbranched polyimide material.
9. The highly heat-resistant hyperbranched polyimide material according to claim 1, wherein the highly heat-resistant hyperbranched polyimide material is applied to the fields of high temperature resistance and gas permeation separation membranes.
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Effective date of registration: 20210705 Address after: 337000 Industrial Park B, Lianhua County, Pingxiang City, Jiangxi Province Patentee after: Jiangxi youze New Material Technology Co.,Ltd. Address before: 412007 No. 88 Taishan Road, Tianyuan District, Zhuzhou City, Hunan Province Patentee before: HUNAN University OF TECHNOLOGY |
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Denomination of invention: Hyperbranched polyimide with high heat resistance and its preparation method and Application Effective date of registration: 20220531 Granted publication date: 20210323 Pledgee: Jiangxi Lianhua rural commercial bank Limited by Share Ltd. Pledgor: Jiangxi youze New Material Technology Co.,Ltd. Registration number: Y2022980006926 |
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