CN117164855A - High-cohesiveness branched polyimide polymer and preparation method thereof - Google Patents

High-cohesiveness branched polyimide polymer and preparation method thereof Download PDF

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Publication number
CN117164855A
CN117164855A CN202311151665.8A CN202311151665A CN117164855A CN 117164855 A CN117164855 A CN 117164855A CN 202311151665 A CN202311151665 A CN 202311151665A CN 117164855 A CN117164855 A CN 117164855A
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anhydride
polyimide polymer
epoxy resin
type epoxy
acid
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陈文博
张振宇
李雪峰
贺小鸽
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Jiangsu Huanfeng Electrical Material Co ltd
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Jiangsu Huanfeng Electrical Material Co ltd
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Abstract

The application discloses a branched polyimide polymer with high cohesiveness, and relates to the field of polyimide preparation. The preparation raw materials comprise: the preparation method comprises the following steps of: dissolving the phenylenediamine substances and the oxygen-containing heterocyclic compound in a solvent, stirring for dissolution and reaction, and then adding the mixture to react with the preparation raw materials. The polyimide polymer is prepared by utilizing multiple step experiments of the phenylenediamine substances and the oxygen-containing heterocyclic compound, has moderate molecular weight, good solubility in polar aprotic solvents and a branched structure, has excellent mechanical property, dimensional stability, cycle stability and heat resistance stability when being used as a binder on the surface of a lithium ion secondary battery current collector, has less capacitance loss and high cycle retention rate, and prolongs the charge and discharge cycle life.

Description

High-cohesiveness branched polyimide polymer and preparation method thereof
Technical Field
The application relates to the field of polyimide preparation, in particular to a branched polyimide polymer with high cohesiveness and a preparation method thereof.
Background
Lithium ion secondary batteries are widely used because of their high energy density, no memory effect, etc., and the binder is an essential component of lithium batteries, and is mainly used to bind active materials and conductive agents together and adhere them to a current collector, so that electrons can flow out or flow to the outside through the active materials, conductive agents, current collectors, and various properties of the binder are also receiving more and more attention. The polymer is an important raw material in the adhesive due to the special structure, wherein polyimide has good thermal stability and chemical stability, low crystallinity and high polarity, is favorable for wetting the organic electrolyte, and can meet the requirement of the lithium battery on the adhesive. However, soluble polyimide is extremely susceptible to swelling in an electrolyte, and when used as a current collector binder, swelling results in poor electrochemical properties and poor adhesion.
Chinese patent application CN110066396 discloses a flexible chain modified polyimide precursor, a preparation method thereof and a lithium ion battery, and by introducing long-chain fatty alcohol, polyalcohol, polysiloxane, polyamine and the like, the flexibility is better, the volume change of a silicon negative electrode in the charge and discharge process is born, the electrochemical performance of the battery is effectively improved when the silicon negative electrode is used as a binder of the lithium ion battery, and the capacity cycle attenuation is reduced. But the heat-resistant stability and dielectric properties of the material are poor. The Chinese patent application CN113629250A provides a polyimide binder for a lithium battery cathode and a silicon-based negative plate, wherein the polyimide binder is prepared by copolymerizing diamine containing imidazole groups, sulfonated diamine and dianhydride containing ketone groups, and imidizing the polyimide binder, has excellent cohesiveness, can inhibit volume expansion in the charge and discharge process, and can further improve the cycle stability.
Chinese patent application CN 114686157a (previous study by the present inventors) discloses a three-dimensional network polymer for adhesives, adding high conductivity materials to polyimide systems to improve the adhesive properties; however, the technology still has the technical problems that the peeling strength is reduced and the weather resistance is to be improved after the technology is applied to a battery assembly for a long time. Based on the above, the inventor further explores to obtain a branched polyimide polymer with high cohesiveness, which can improve the cohesive strength of polyimide on one hand and the service performance of a battery on the other hand.
Disclosure of Invention
The application provides a branched polyimide polymer with high cohesiveness and a preparation method thereof, which solves the problems of insufficient cohesiveness, poor cycle stability and high volume expansion rate when polyimide is used for anode and cathode materials of batteries in the prior art, and realizes a polyimide binder with high cohesiveness, stable size and good electrical property.
The first aspect of the application provides a highly adhesive branched polyimide polymer, which is prepared from the following raw materials: the organic compound comprises phenylenediamine substances, oxygen-containing heterocyclic compounds, polyamino organic substances, compounds containing active groups, end capping agents, medium-high boiling point solvents, thermosetting resins and aprotic solvents.
In some preferred embodiments, the phenylenediamine-containing material is selected from one or more of o-phenylenediamine, 1, 4-phenylenediamine, 1,2, 4-triaminobenzene, 1,3, 5-triaminobenzene, 2-amino-4-methyl-6-nitrobenzoic acid, 4-amino-2-fluoro-5-methoxybenzoic acid; preferably, the phenylenediamine-containing substance is 1,3, 5-triaminobenzene.
In some preferred embodiments, the oxygen-containing heterocyclic compound is selected from one or more of succinic anhydride, hexafluorodianhydride, maleic anhydride, oxalic anhydride, 4' -oxo-phthalic anhydride, butanetetracarboxylic anhydride, 3',4, ' -4-diphenyl sulfone tetracarboxylic anhydride, p-phenyl bis (trimellitate) dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic anhydride, trimellitic anhydride acid chloride, 4, 5-difluoro-phthalic anhydride; preferably, the oxygen-containing heterocyclic compound is selected from one or more of hexafluorodianhydride, 4' -oxo-phthalic anhydride, 3',4, ' 4-benzophenone tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride and trimellitic anhydride acid chloride; further preferably, the oxygen-containing heterocyclic compound is one or more of 2, 3',4' -diphenyl ether tetracarboxylic dianhydride and trimellitic anhydride acid chloride.
When the polyimide binder is used as a battery, the polyimide binder is inevitably reduced in the first-cycle discharge process, but the inventor finds that the oxygen-containing heterocyclic compound containing diphenyl ether groups or benzophenone groups is selected, so that the elasticity of the synthesized polyimide is obviously enhanced, the complete electrode structure is favorably maintained, and the cycle stability of the polyimide is further improved. The possible reason is presumed that when the phenyl diamine-containing substance is 1,3, 5-triaminobenzene, the carbon-carbon bond in the benzene ring is a unique bond between a single bond and a double bond, the three amino substituents are all meta-substituted, the structure is stable, the reactivity is high, the amidation reaction can well occur with the oxygen-containing heterocyclic compound to generate an amide bond and a carboxyl group, meanwhile, the C-N single bond can also be protected by a five-membered ring, the bond energy is improved, the intermolecular acting force is enhanced, the structure of the polymer is further protected, the thermal stability and toughness of the polyimide polymer are improved, the structural integrity of the electrode is still maintained in the use and heating process of the battery, the cyclic stability is improved, and the cycle life is prolonged. Particularly, when the oxygen-containing heterocyclic compound is 2, 3',4' -diphenyl ether tetracarboxylic dianhydride or trimellitic anhydride acyl chloride, the mechanical strength of the polyimide can be enhanced, and the dimensional stability, chemical corrosion resistance and hydrolysis resistance of the polyimide can be obviously improved.
In some preferred embodiments, the polyamino organic is selected from one or more of ethylenediamine, propylenediamine, propyltriamine, 4-aminobenzophenone, 4 '-diaminodiphenyl ether, 2-amino-4-bromobenzophenone, 3' -diamino-4, 4 '-difluorobenzophenone, 3, 4-diaminobenzophenone, 3, 4-tetraminobenzophenone, 2-aminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4-amino-4' -tert-butyldiphenyl ether; preferably, the polyamino organic matter is selected from one or more of propylene diamine, 4' -diaminodiphenyl ether, 3' -diamino-4, 4' -difluorobenzophenone; further preferably, the polyamino organic compound is 3,3 '-diamino-4, 4' -difluorobenzophenone.
In some preferred embodiments, the reactive group-containing compound is selected from one or more of 4-amino-1, 8-naphthalene dicarboxylic anhydride, 4-dimethylaminobenzoic anhydride, 4-amino-3-sulfo-1, 8-naphthalene dicarboxylic anhydride, 4-diaminodiphenyl ether, 3-hydroxy-3-methylpentanedioic anhydride, 4-hydroxy-1, 8-naphthalene dicarboxylic anhydride, 2-hydroxycinnamate anhydride, trimellitic anhydride, 5-endo-carboxyoxaziridine anhydride; further preferably, the compound containing reactive groups is selected from one or more of 4, 4-diaminodiphenyl ether, 2-hydroxycinnamate, trimellitic anhydride.
The oxygen-containing heterocyclic compound containing diphenyl ether or diphenyl ketone structure is selected in the system, and can improve the mechanical strength and dimensional stability of polyimide, but the introduction of polar groups such as carbonyl and ether bonds can increase the electron cloud density of the polar groups, so that the dielectric constant and dielectric loss are increased. The inventors have found that the addition of a compound containing reactive groups to the above system can effectively prevent the deterioration of the dielectric properties of the polyimide polymer. Presumably, the reason is that the ether bond and the adjacent benzene ring in the acid anhydride containing diphenyl ether or benzophenone groups can form a conjugated system, the carbonyl is a part of a five-membered ring system, the carbonyl can further react with amino in the system to generate more amide bonds and carboxyl groups, the active reactive groups of the system are increased, a branched structure is formed, the arrangement mode of molecular chains in polyamide acid in different directions is improved, intermolecular gaps are increased while strong intermolecular force is provided, the dielectric constant is further reduced, the mechanical strength of the polyimide polymer is further enhanced, and the micropore structure formed by branching can effectively reduce the internal resistance of the ion migration process, further reduce the huge volume expansion effect of the ion migration process, and avoid pulverization of electrode materials or the falling phenomenon from a current collector.
In some preferred embodiments, the capping agent is selected from one or more of maleic anhydride, norbornene dianhydride, phenylethynyl phthalic anhydride, para-aminobenzoic acid, para-aminophenylacetic acid, 3-fluoro-4-aminobenzoic acid, 3-nitro-4-aminobenzoic acid, para-aminosalicylic acid.
In some preferred embodiments, the medium-high boiling point solvent is selected from one or more of xylene, acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, aromatic monocarboxylic acid anhydride; preferably, the medium-high boiling point solvent is selected from one or more of xylene and acetic anhydride.
In some preferred embodiments, the thermosetting resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether type epoxy resin, glycidyl ester type epoxy resin; preferably, the thermosetting resin is selected from one or more of bisphenol A type epoxy resin, glycidyl ester type epoxy resin, aliphatic glycidyl ether type epoxy resin and bisphenol F type epoxy resin; further preferably, the thermosetting resin is preferably bisphenol F type epoxy resin.
In some preferred embodiments, the bisphenol F type epoxy resin has an epoxy value of 0.1 to 0.6mol/100g; preferably, the bisphenol F type epoxy resin has an epoxy value of 0.12 to 0.55mol/100g.
The inventor discovers that the molecular chain in the added oxygen-containing heterocyclic compound containing diphenyl ether or diphenyl ketone structure has great rigidity, and the polyimide has large steric hindrance and strong intermolecular acting force, which can cause the molding and processing difficulties of polyimide and poor dissolution performance. But the solubility and processability thereof can be improved by adding a thermosetting resin, particularly an epoxy resin. The probable reason is presumed that the epoxy resin is a non-coplanar, twistable structure, which can react with the epoxy ring-opening reaction of the active group in the hard segment structure containing diphenyl ether or diphenyl ketone in the system, thereby reducing the intermolecular acting force and further improving the solubility of polyimide. And simultaneously, the copolymer has synergistic effect with anhydride in the system, which is beneficial to increasing the solubility of the copolymer and promoting the formation of hydrogen bonds so as to increase the adhesiveness. In addition, the epoxy resin has a molecular chain portion with high adhesion at the end of the polymer structure, which can improve the adhesion of the polymer on the surface of the current collector and exhibit high adhesion strength. The inventors have unexpectedly found that when the thermosetting resin is bisphenol F type epoxy resin and the epoxy value is 0.12 to 0.55mol/100g, a network structure can be formed after the thermosetting resin is mixed with the positive electrode or negative electrode active material, and the adhesiveness, dielectric property and cycle stability of the obtained polymer can be further improved, and particularly, the effect of the thermosetting resin serving as a positive electrode binder is optimal.
In some preferred embodiments, the aprotic solvent is selected from one or more of NMP (nitrogen-methylpyrrolidone), DMF (N, N-dimethylformamide), DMAC (dimethylacetamide), EC (ethylene carbonate), PC (propylene carbonate).
In some preferred embodiments, the highly adhesive branched polyimide features are shown in formula 1:
wherein the R chain consists of a chain segment 1 and a chain segment 2, and is specifically shown as a formula 2:
the A structure comprises
The B structure includes-NH 2 One or more of-OH, COOH.
The D structure is a molecular chain containing one or more epoxy groups.
The second aspect of the application provides a method for preparing a highly adhesive branched polyimide polymer, comprising the steps of:
(1) Dissolving a phenylenediamine substance and an oxygen-containing heterocyclic compound in an aprotic solvent under the atmosphere of nitrogen, stirring and dissolving, and reacting;
(2) Continuously adding polyamino organic matters, compounds containing active groups and end capping agents into the step (1) to obtain an oligomer solution;
(3) Adding a medium-high boiling point solvent into the oligomer solution obtained in the step (2), heating for reaction, and then purifying and drying to obtain intermediate product powder;
(4) Dispersing the powder obtained in the step (3) in an aprotic solvent, and adding thermosetting resin to obtain the polyimide polymer.
The beneficial effects are that:
the polyimide polymer is prepared by utilizing multiple step experiments of the phenylenediamine substances and the oxygen-containing heterocyclic compounds, has moderate molecular weight, good solubility in polar aprotic solvents, has a branched structure, has excellent mechanical property, dimensional stability, cyclic stability and heat resistance stability when being used as a binder on the surface of a lithium ion secondary battery current collector, and contains a high-cohesiveness molecular chain and a microporous structure, so that the binding fastness and the volume expansion effect are greatly improved, the pulverization of an electrode material or the shedding phenomenon from the current collector is avoided, the intercalation/intercalation of lithium ions is facilitated, the performance of an active material is fully exerted, the conductivity is good, the capacitance loss is less in the cyclic charge and discharge process, the cyclic retention rate is high, the charge and discharge cycle life is prolonged, the use safety is improved, and the use cost is reduced.
Detailed Description
Example 1.
1. The polyimide polymer is prepared from the following raw materials: the organic compound comprises phenylenediamine substances, oxygen-containing heterocyclic compounds, polyamino organic substances, compounds containing active groups, end capping agents, medium-high boiling point solvents, thermosetting resins and aprotic solvents.
The phenyl diamine-containing substance is 1,3, 5-triaminobenzene.
The oxygen-containing heterocyclic compound is 2, 3',4' -diphenyl ether tetracarboxylic dianhydride.
The polyamino organic matter is 3,3 '-diamino-4, 4' -difluorobenzophenone.
The compound containing active groups is 2-hydroxy cinnamic anhydride.
The end capping agent is p-aminosalicylic acid.
The medium-high boiling point solvent is m-xylene.
The thermosetting resin is bisphenol F type epoxy resin.
The epoxy value of the bisphenol F type epoxy resin is 0.48-0.54 mol/100g (NPEF-164X in south Asia of Taiwan).
The aprotic solvent is NMP.
2. A method for preparing a branched polyimide polymer with high cohesiveness, comprising the following steps:
(1) Dissolving 0.01mol of phenylenediamine substances and 0.03mol of oxygen-containing heterocyclic compounds in 400mL of aprotic solvent under the atmosphere of nitrogen, stirring and dissolving, and reacting for 3h;
(2) Continuously adding 0.03mol of polyamino organic matters, 0.03mol of compounds containing active groups and 0.03mol of blocking agents into the step (1) respectively and reacting for 3 hours to obtain an oligomer solution;
(3) Adding 200mL of medium-high boiling point solvent into the oligomer solution obtained in the step (2), heating to 170 ℃ for reaction for 5.5h, and then purifying and drying to obtain intermediate product powder;
(4) Dispersing the powder obtained in the step (3) in an aprotic solvent, and adding thermosetting resin to obtain the polyimide polymer.
The weight ratio of the powder obtained in the step (3) to the thermosetting resin is 1:1.2.
the mass concentration of the powder obtained in the step (3) is 30g/L.
Example 2:
1. a highly adhesive branched polyimide polymer differing from example 1 in that:
the bisphenol F type epoxy resin has an epoxy value of 0.22 to 0.26mol/100g (Henschel model: ARALDITE GY 281).
2. A process for preparing a branched polyimide polymer having high adhesion, which differs from example 1 in that
The method comprises the following steps:
the weight ratio of the powder obtained in the step (3) to the thermosetting resin is 5:4.
comparative example 1:
1. a highly adhesive branched polyimide polymer differing from example 2 in that:
the compound containing active groups is hydroquinone.
2. A process for preparing a highly adhesive branched polyimide polymer, as in example 2.
Comparative example 2:
1. a highly adhesive branched polyimide polymer differing from example 2 in that:
the epoxy value of the bisphenol F type epoxy resin is 0.58-0.61 mol/100g (5-5 Taiwan south Asia, brand: NPEF-500).
2. A process for preparing a highly adhesive branched polyimide polymer, as in example 2.
Performance test:
sample preparation: assembling the anode, the cathode, the electrolyte and the diaphragm into a battery;
and (3) a positive electrode: adding the polymers obtained in the examples and the comparative examples into an organic solvent NMP (mass concentration is 0.03 g/mL), then adding 40g of positive electrode active material, stirring uniformly, coating the mixture on the surface of a current collector, and reacting at 180 ℃ for 0.5h to obtain a battery positive electrode plate; wherein the positive electrode active material is LiNi 0.6 Mn 0.2 Co 0.2 O 2 And (3) particles.
And (3) a negative electrode: consists of graphite (94.5 percent by weight), conductive carbon black (1.0 percent by weight), a negative electrode binder (CMC) (2.25 percent by weight) and the balance of water;
the electrolyte is LiPF 6 Wherein LiPF is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate 6 The concentration of (2) is 1M, and the volume ratio of the ethylene carbonate, the dimethyl carbonate and the methyl ethyl carbonate is 1:1:2;
the membrane is Celgard 2400.
1. Peel strength: the prepared positive pole pieceRolling to obtain a strip with a size of 20.0cm×2.5cm, attaching a current collector to a steel plate with a thickness of 1mm with double-sided TAPE, attaching a transparent adhesive TAPE (NITTO TAPE) to the coated layer, peeling at a speed of 100mm/min and a direction of 180 ° with a tensile tester, testing three times, and averaging to obtain a measured adhesive force N 0 。
The positive pole piece is put into a high-low temperature circulation test box to circulate 150 times (respectively at-5 ℃,25 ℃ and 50 ℃ for 2 hours respectively, recorded as 1 circulation), and is treated in the same treatment mode after being taken out, and the cohesive force N is measured again 1 The method comprises the steps of carrying out a first treatment on the surface of the The decrease rate (%) of the adhesion after the cycle was calculated.
3. First charge capacity: the first charge capacity of the battery was read after the positive electrode tab was subjected to a charge test using a battery tester (new-wire cell tester CT-4008Tn-5V10 mA-164). Wherein the charge-discharge voltage was set to 3V and the charge-discharge current was set to 50mA/g.
4. First coulombic efficiency: and reading the first charge and discharge capacity of the battery after performing charge and discharge test on the positive electrode plate by using a battery tester. Wherein the charge-discharge voltage was set to 3V and the charge-discharge current was set to 50mA/g.
5. 0.5C charge-discharge 100 times capacity retention rate: the lithium ion battery is prepared, the sample is charged at 20 ℃ under constant current of 0.5C until the voltage reaches 4.2V, the cut-off current is 0.03C, the sample is electrically placed for 15min (which means that the sample is stopped at the step of standing for 15min after the battery finishes charging work, and then a discharge test is carried out after the inside of the battery is stable), the lithium ion battery is discharged to 3.0V under constant current of 5C at 20 ℃, and can be placed for 30min during charge-discharge conversion, 100 times are carried out in total, the cycle capacity is tested, and the capacitance retention rate is calculated.
Results of Performance test of examples and comparative examples

Claims (8)

1. The branched polyimide polymer with high cohesiveness is characterized in that the preparation raw materials of the polyimide polymer comprise: a phenylenediamine substance, an oxygen-containing heterocyclic compound, a polyamino organic substance, a compound containing active groups, a blocking agent, a medium-high boiling point solvent, a thermosetting resin and an aprotic solvent;
the compound containing active groups is selected from one or more of 4-amino-1, 8-naphthalene dicarboxylic acid anhydride, 4-dimethylamino benzoic acid anhydride, 4-amino-3-sulfo-1, 8-naphthalene dicarboxylic acid anhydride, 4-diamino diphenyl ether, 3-hydroxy-3-methyl glutaric acid anhydride, 4-hydroxy-1, 8-naphthalene dicarboxylic acid anhydride, 2-hydroxy cinnamic acid anhydride, trimellitic acid anhydride and 5-in-carboxyl oxadiazonium acid anhydride;
the thermosetting resin is bisphenol F type epoxy resin; the epoxy value of the bisphenol F type epoxy resin is 0.1-0.6 mol/100g.
2. The highly adhesive branched polyimide polymer according to claim 1, wherein the phenylenediamine-containing substance is one or more selected from the group consisting of o-phenylenediamine, 1, 4-phenylenediamine, 1,2, 4-triaminobenzene, 1,3, 5-triaminobenzene, 2-amino-4-methyl-6-nitrobenzoic acid, and 4-amino-2-fluoro-5-methoxybenzoic acid.
3. A highly adhesive branched polyimide polymer according to claim 1, wherein the oxygen-containing heterocyclic compound is selected from the group consisting of succinic anhydride, hexafluorodianhydride, maleic anhydride, oxalic anhydride, 4' -oxyphthalic anhydride, butanetetracarboxylic dianhydride, 3',4, one or more of ' 4-diphenyl sulfone tetracarboxylic dianhydride, p-phenyl bis (trimellitate) dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, trimellitic anhydride acid chloride, 4, 5-difluorophthalic anhydride.
4. A highly adhesive branched polyimide polymer according to claim 1 or 3, wherein the oxygen-containing heterocyclic compound is one or more of 2, 3',4' -diphenyl ether tetracarboxylic dianhydride, trimellitic anhydride acid chloride.
5. The highly adhesive branched polyimide polymer of claim 1, wherein the polyamino organic compound is selected from one or more of ethylenediamine, propylenediamine, propyltriamine, 4-aminobenzophenone, 4 '-diaminodiphenyl ether, 2-amino-4-bromobenzophenone, 3' -diamino-4, 4 '-difluorobenzophenone, 3, 4-diaminobenzophenone, 3, 4-tetraminobenzophenone, 2-aminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4-amino-4' -tert-butyldiphenyl ether.
6. The highly adhesive branched polyimide polymer according to claim 1, wherein the end-capping agent is one or more selected from the group consisting of maleic anhydride, norbornene dianhydride, phenylethynyl phthalic anhydride, para-aminobenzoic acid, para-aminophenylacetic acid, 3-fluoro-4-aminobenzoic acid, 3-nitro-4-aminobenzoic acid, para-aminosalicylic acid.
7. The highly adhesive branched polyimide polymer according to claim 1, wherein the thermosetting resin is one or more selected from bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether type epoxy resin, glycidyl ester type epoxy resin; preferably, the thermosetting resin is selected from one or more of bisphenol a type epoxy resin, glycidyl ester type epoxy resin, aliphatic glycidyl ether type epoxy resin, bisphenol F type epoxy resin.
8. A process for the preparation of a highly adhesive branched polyimide polymer according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1) Dissolving a phenylenediamine substance and an oxygen-containing heterocyclic compound in an aprotic solvent under the atmosphere of nitrogen, stirring and dissolving, and reacting;
(2) Continuously adding polyamino organic matters, compounds containing active groups and end capping agents into the step (1) to obtain an oligomer solution;
(3) Adding a medium-high boiling point solvent into the oligomer solution obtained in the step (2), heating for reaction, and then purifying and drying to obtain intermediate product powder;
(4) Dispersing the powder obtained in the step (3) in an aprotic solvent, and adding thermosetting resin to obtain the polyimide polymer.
CN202311151665.8A 2023-09-07 2023-09-07 High-cohesiveness branched polyimide polymer and preparation method thereof Pending CN117164855A (en)

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