CN114702671A - Carboxylated crosslinked polyimide prepolymer and preparation method thereof - Google Patents
Carboxylated crosslinked polyimide prepolymer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the field of C09D179/08, in particular to a carboxylated crosslinked polyimide prepolymer and a preparation method thereof, wherein the carboxylated crosslinked polyimide prepolymer comprises 30-50 parts of carboxyl diamine, 70-90 parts of rigid diamine, 180-220 parts of anhydride, 50-70 parts of chain extender, 30-40 parts of crosslinking monomer, 200 parts of solvent and 50-60 parts of functional additive, so that the provided polyimide prepolymer has excellent thermal stability and mechanical properties, improved processability and convenient subsequent application in bonding of electrode plates in lithium ion batteries, and has high practical popularization and application values.
Description
Technical Field
The invention relates to the field of C09D179/08, in particular to a carboxylated crosslinked polyimide prepolymer and a preparation method thereof.
Background
Polyimide (Polyimide) is a high molecular polymer containing an imide ring structure in a molecular main chain, has excellent mechanical property, electrical property, radiation resistance and heat resistance, is widely applied to various fields at present, and Polyimide resin and a composite material thereof are applied to the fields of flexible screens, rail transit, aerospace, fireproof and flame-retardant, photoresist, electronic packaging, fan blades, automobiles, weaponry and the like by using form materials such as films, fibers, foams, coatings, adhesives and the like. However, due to the rigidity of the polyimide molecular chain and strong interaction between molecules, many aromatic polyamides are insoluble and infusible, so that the subsequent processing is difficult, and particularly when the polyimide is used as a binder for a lithium ion battery, the electrochemical performance of the battery is seriously influenced.
In order to improve the processing performance of the existing polyimide, researchers introduce flexible groups such as ether bonds, sulfone groups, alkyl groups, siloxane groups and the like into a polyimide molecular structure through molecular structure design to improve the flexibility of molecular chains and reduce the interaction between the molecular chains, chinese patent CN103649174B discloses a cross-linked polyimide resin, a manufacturing method thereof, a binder resin composition and application thereof, wherein polyimide siloxane with ketone groups reacts with diamine to prepare cross-linked polyimide, but the introduction of the flexible groups causes the reduction of the thermal stability and the mechanical property of the polyimide, thereby greatly limiting the application of the polyimide in the field of lithium ion batteries.
Therefore, the provided carboxylated crosslinked polyimide prepolymer has excellent thermal stability and mechanical property, improved processing performance, and convenient subsequent application in bonding of electrode plates in lithium ion batteries, and has high practical popularization and application values.
Disclosure of Invention
The invention provides a carboxylated crosslinked polyimide prepolymer, which at least comprises the following preparation raw materials in parts by weight: 30-50 parts of carboxyl-containing diamine, 70-90 parts of rigid diamine, 180-220 parts of anhydride, 50-70 parts of chain extender, 30-40 parts of crosslinking monomer, 150-200 parts of solvent and 50-60 parts of functional assistant.
In a preferred embodiment, the rigid diamine is at least one selected from the group consisting of m-phenylenediamine, 4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl ether, 4' -diaminodiphenylmethane, and 2- (4-aminophenyl) -5-aminobenzimidazole. Preferably, the rigid diamine is 2- (4-aminophenyl) -5-aminobenzimidazole;
as a preferable embodiment, the diamine containing a carboxyl group is at least one selected from the group consisting of 2, 5-diaminoterephthalic acid, 3, 4-diaminobenzoic acid, 3, 5-diamino-4-methylbenzoic acid, and 3, 5-dimethyl-2-aminobenzoic acid; preferably, the carboxyl group-containing diamine is 2, 5-diaminoterephthalic acid or 3, 5-dimethyl-2-aminobenzoic acid;
as a preferable technical scheme, the mass ratio of the diamine containing carboxyl and the diamine containing rigidity is (30-40): (80-90);
in the process of research, the inventor finds that not all rigid diamines and carboxyl group-containing diamines can be used in combination to perform polycondensation with acid anhydride, and based on the system of the invention, by using 2- (4-aminophenyl) -5-aminobenzimidazole and 2, 5-diaminoterephthalic acid or 3, 5-dimethyl-2-aminobenzoic acid as the diamine raw material of polyimide, the mass ratio of the carboxyl group-containing diamine to the rigid diamine is controlled to be (30-40): (80-90), so that the provided carboxylated crosslinked polyimide prepolymer has excellent high temperature resistance and lower shrinkage, the thermal stability of the polyimide is ensured, and the subsequent processing and application are facilitated.
As a preferred embodiment, the acid anhydride is at least one selected from the group consisting of cyclobutanetetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, and 1,4,5, 8-naphthalenetetracarboxylic anhydride; preferably, the acid anhydride is 3,3',4,4' -biphenyl tetracarboxylic dianhydride or 3,3',4,4' -benzophenone tetracarboxylic dianhydride;
as a preferred technical scheme, the chain extender is aliphatic dianhydride or aliphatic diacid chloride; preferably, the chain extender is aliphatic diacid chloride; preferably, the aliphatic diacid chloride is selected from at least one of malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride and sebacoyl chloride; preferably, the aliphatic diacid chloride is malonyl chloride.
In the prior art, in order to improve the processing performance of the existing polyimide, flexible groups such as ether bond, sulfuryl, alkyl, siloxy and the like are introduced into the molecular structure of the polyimide to improve the flexibility of molecular chains and reduce the interaction among the molecular chains, however, the introduction of the flexible group reduces the mechanical property and the heat resistance of the polyimide to a certain extent, and limits the application of the polyimide in the field of lithium ion batteries, and the inventor surprisingly finds that after the diamine and the anhydride in the system are subjected to polycondensation reaction and are capped by the diamine, aliphatic diacid chloride, especially micromolecular malonyl chloride, can minimize the reduction of the mechanical property and the heat resistance of the polyimide caused by the introduction of the flexible chain segment, and meanwhile, the processing performance of polyimide is effectively improved, and the subsequent electrode plate is convenient to bond and process.
As a preferred technical solution, the crosslinking monomer is selected from at least one of aziridine, isocyanate, bisphenol a epoxy resin, aliphatic diamine, and aromatic diamine; preferably, the crosslinking monomer is aziridine. Based on the system, aziridine is adopted as a crosslinking monomer, so that the binding effect between the polyimide and the silicon-based electrode active substance is improved, and the mechanical property and the heat resistance of the polyimide are ensured. The inventor speculates that the system uses diamine containing carboxyl as one of raw materials, and the diamine and anhydride containing carboxyl carry out polycondensation reaction, the generated polymer structure contains a large amount of carboxyl, the carboxyl existing in the polymer structure can be crosslinked with aziridine to form a stable network structure, the mechanical property and the heat resistance of polyimide are ensured, and meanwhile, the carboxyl in the polymer structure and a silicon-based electrode active material have strong bonding effect, and the quality of an electrode plate is ensured.
As a preferred technical scheme, the solvent is at least one selected from tetrahydrofuran, N-methyl pyrrolidone, N-methyl formamide, N-dimethyl acetamide and dimethyl sulfoxide; preferably, the solvent is N, N-dimethylacetamide;
as a preferable technical scheme, the functional assistant is picoline and acetic anhydride, and the mass ratio of the picoline to the acetic anhydride is (0.8-1.2): (4-6);
the invention also provides a preparation method of the carboxylated crosslinked polyimide prepolymer, which at least comprises the following steps:
(1) adding diamine containing carboxyl and rigid diamine into a solvent for dissolving, and then adding anhydride for polycondensation reaction for 10-12 h;
(2) then adding a chain extender for further chain extension reaction for 3-5h, and then adding a functional auxiliary agent for imidization reaction for 24 h;
(3) then adding a crosslinking monomer to carry out crosslinking reaction for 1-2h, and then heating and drying at the temperature of 180-200 ℃ for 5-6h to obtain the product.
Advantageous effects
1. The invention provides a carboxylated crosslinked polyimide prepolymer, which has excellent thermal stability and mechanical property and improved processability, is convenient to be subsequently applied to bonding of electrode plates in lithium ion batteries, and has high practical popularization and application values.
2. Based on the system, 2- (4-aminophenyl) -5-aminobenzimidazole and 2, 5-diaminoterephthalic acid or 3, 5-dimethyl-2-aminobenzoic acid are adopted as diamine raw materials of polyimide together, and particularly, the mass ratio of the diamine containing carboxyl groups to the rigid diamine is controlled to be (30-40): (80-90), so that the provided carboxylated crosslinked polyimide prepolymer has excellent high temperature resistance and lower shrinkage, the thermal stability of the polyimide is ensured, and the subsequent processing and application are facilitated.
3. The diamine and the anhydride in the system are subjected to polycondensation reaction and terminated by the diamine, and then the aliphatic diacid chloride, especially the micromolecule malonyl chloride, is introduced, so that the reduction of the mechanical property and the heat resistance of the polyimide caused by the introduction of the flexible chain segment is minimized, the processability of the polyimide is effectively improved, and the subsequent electrode plate can be bonded and processed conveniently.
4. Based on the system, aziridine is adopted as a crosslinking monomer, so that the binding effect between the polyimide and the silicon-based electrode active substance is improved, and the mechanical property and the heat resistance of the polyimide are ensured.
Detailed Description
Example 1
In one aspect, embodiment 1 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is prepared from the following raw materials in parts by weight: 35 parts of carboxyl-containing diamine, 85 parts of rigid diamine, 200 parts of anhydride, 60 parts of chain extender, 35 parts of crosslinking monomer, 180 parts of solvent and 55 parts of functional assistant.
The rigid diamine is 2- (4-aminophenyl) -5-aminobenzimidazole;
the diamine containing carboxyl is 2, 5-diamino terephthalic acid;
the mass ratio of the carboxyl-containing diamine to the rigid diamine is 35: 85 parts by weight;
the acid anhydride is 3,3',4,4' -biphenyl tetracarboxylic dianhydride;
the chain extender is aliphatic diacid chloride; the aliphatic diacid chloride is malonyl chloride.
The crosslinking monomer is aziridine.
The solvent is N, N-dimethylacetamide;
the functional assistant is picoline and acetic anhydride, and the mass ratio of the picoline to the acetic anhydride is 1: 5;
in another aspect, embodiment 1 of the present invention provides a method for preparing a carboxylated crosslinked polyimide prepolymer, including the following steps:
(1) adding diamine containing carboxyl and rigid diamine into a solvent for dissolving, and then adding anhydride for polycondensation reaction for 12 hours;
(2) then adding a chain extender for further chain extension reaction for 5 hours, and then adding a functional auxiliary agent for imidization reaction for 24 hours;
(3) and then adding a crosslinking monomer for crosslinking reaction for 1h, and then heating and drying at 200 ℃ for 6h to obtain the modified polyurethane.
Example 2
In one aspect, embodiment 2 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is prepared from the following raw materials in parts by weight: 40 parts of carboxyl-containing diamine, 90 parts of rigid diamine, 220 parts of anhydride, 70 parts of chain extender, 40 parts of crosslinking monomer, 200 parts of solvent and 60 parts of functional assistant.
The rigid diamine is 2- (4-aminophenyl) -5-aminobenzimidazole;
the diamine containing carboxyl is 3, 5-dimethyl-2-aminobenzoic acid;
the mass ratio of the carboxyl-containing diamine to the rigid diamine is 40: 60, adding a solvent to the mixture;
the acid anhydride is 3,3',4,4' -benzophenone tetracarboxylic dianhydride;
the chain extender is aliphatic diacid chloride; the aliphatic diacid chloride is malonyl chloride.
The crosslinking monomer is aziridine.
The solvent is N, N-dimethylacetamide;
the functional assistant is picoline and acetic anhydride, and the mass ratio of the picoline to the acetic anhydride is 1.2: 6;
in another aspect, embodiment 2 of the present invention provides a method for preparing a carboxylated crosslinked polyimide prepolymer, including the following steps:
(1) adding diamine containing carboxyl and rigid diamine into a solvent for dissolving, and then adding anhydride for polycondensation reaction for 12 hours;
(2) then adding a chain extender for further chain extension reaction for 5 hours, and then adding a functional auxiliary agent for imidization reaction for 24 hours;
(3) and then adding a crosslinking monomer for crosslinking reaction for 1h, and then heating and drying at 200 ℃ for 6h to obtain the modified polyurethane.
Example 3
In one aspect, embodiment 3 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is prepared from the following raw materials, by weight: 30 parts of carboxyl-containing diamine, 80 parts of rigid diamine, 180 parts of anhydride, 50 parts of chain extender, 30 parts of crosslinking monomer, 150 parts of solvent and 50 parts of functional assistant.
The rigid diamine is 2- (4-aminophenyl) -5-aminobenzimidazole;
the diamine containing carboxyl is 2, 5-diamino terephthalic acid;
the mass ratio of the diamine containing carboxyl to the rigid diamine is (30-40): (80-90);
the acid anhydride is 3,3',4,4' -benzophenone tetracarboxylic dianhydride;
the chain extender is aliphatic diacid chloride; the aliphatic diacid chloride is malonyl chloride.
The crosslinking monomer is aziridine.
The solvent is N, N-dimethylacetamide;
the functional assistant is picoline and acetic anhydride, and the mass ratio of the picoline to the acetic anhydride is 0.8: 4;
in another aspect, embodiment 3 of the present invention provides a method for preparing a carboxylated crosslinked polyimide prepolymer, including the following steps:
(1) adding diamine containing carboxyl and rigid diamine into a solvent for dissolving, and then adding anhydride for polycondensation reaction for 12 hours;
(2) then adding a chain extender for further chain extension reaction for 5 hours, and then adding a functional auxiliary agent for imidization reaction for 24 hours;
(3) and then adding a crosslinking monomer for crosslinking reaction for 1h, and then heating and drying at 200 ℃ for 6h to obtain the modified polyurethane.
Comparative example 1
Comparative example 1 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is the same as example 1 except that the aliphatic diacid chloride is sebacoyl chloride.
Comparative example 2
Comparative example 2 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is the same as example 1 except that the crosslinking monomer is ethylenediamine.
Comparative example 3
Comparative example 3 of the present invention provides a carboxylated crosslinked polyimide prepolymer, which is the same as example 1 except that the mass ratio of the carboxyl group-containing diamine to the rigid diamine is 60: 30.
performance test method
(1) The shrinkage of the carboxylated crosslinked polyimide prepolymers prepared in examples and comparative examples was measured with reference to standard astm d 955;
(2) the tensile strength of the carboxylated crosslinked polyimide prepolymers prepared in the examples and the comparative examples was measured with reference to standard astm d 638;
(3) the impact strength of the carboxylated cross-linked polyimide prepolymers prepared in the examples and the comparative examples was measured with reference to standard astm d 256;
(4) the heat distortion temperature of the carboxylated cross-linked polyimide prepolymers prepared in the examples and the comparative examples is measured under 1.82MPa according to the standard ASTMD 648;
2. the carboxylated cross-linked polyimide prepolymers prepared in the examples and the comparative examples are prepared into silicon-based negative pole pieces according to the following method, the silicon-based negative pole pieces are assembled into a battery, the peel strength of the silicon-based negative pole pieces, the swelling ratio of the pole pieces and the electrochemical performance of the battery are tested, and the performance test results are shown in table 1.
Preparing a negative pole piece: adding 6 parts by weight of carboxylated crosslinked polyimide prepolymer, 15 parts by weight of silicon-carbon active material and 5 parts by weight of Ketjen black into 100 parts by weight of N-methyl-2-pyrrolidone, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, drying at 80 ℃ for 12 hours, and performing punch forming to obtain the silicon-based negative electrode piece.
Assembling the negative pole piece and the LFP positive pole piece into a battery, wherein the battery electrolyte is LiPF6A mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
Claims (10)
1. A carboxylated cross-linked polyimide prepolymer is characterized by at least comprising the following preparation raw materials in parts by weight: 30-50 parts of carboxyl-containing diamine, 70-90 parts of rigid diamine, 180-220 parts of anhydride, 50-70 parts of chain extender, 30-40 parts of crosslinking monomer, 200 parts of solvent and 50-60 parts of functional assistant.
2. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein the rigid diamine is at least one selected from the group consisting of m-phenylenediamine, 4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl ether, 4' -diaminodiphenylmethane, and 2- (4-aminophenyl) -5-aminobenzimidazole.
3. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein the diamine containing carboxyl groups is at least one member selected from the group consisting of 2, 5-diaminoterephthalic acid, 3, 4-diaminobenzoic acid, 3, 5-diamino-4-methylbenzoic acid, and 3, 5-dimethyl-2-aminobenzoic acid.
4. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein the mass ratio of the diamine containing carboxyl groups to the rigid diamine is (30-40): (80-90).
5. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein said acid anhydride is at least one selected from the group consisting of cyclobutanetetracarboxylic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, and 1,4,5, 8-naphthalenetetracarboxylic anhydride.
6. The carboxylated crosslinked polyimide prepolymer according to claim 5, wherein the acid anhydride is 3,3',4,4' -biphenyltetracarboxylic dianhydride or 3,3',4,4' -benzophenonetetracarboxylic dianhydride.
7. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein the chain extender is aliphatic dianhydride or aliphatic diacid chloride.
8. The carboxylated crosslinked polyimide prepolymer according to claim 1, wherein the crosslinking monomer is at least one selected from the group consisting of aziridine, isocyanate, bisphenol a epoxy resin, aliphatic diamine, and aromatic diamine.
9. The carboxylated crosslinked polyimide prepolymer according to claim 8, wherein the solvent is at least one selected from the group consisting of tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, N-dimethylacetamide, and dimethylsulfoxide.
10. A method for preparing a carboxylated crosslinked polyimide prepolymer according to any one of claims 1 to 9, comprising at least the following steps:
(1) adding diamine containing carboxyl and rigid diamine into a solvent for dissolving, and then adding anhydride for polycondensation reaction for 10-12 h;
(2) then adding a chain extender for further chain extension reaction for 3-5h, and then adding a functional auxiliary agent for imidization reaction for 24 h;
(3) then adding a crosslinking monomer to carry out crosslinking reaction for 1-2h, and then heating and drying at the temperature of 180-200 ℃ for 5-6h to obtain the product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728697A (en) * | 1985-09-27 | 1988-03-01 | General Electric Company | Novel copolyamideimides, prepolymers therefor and method for their preparation |
| CN107261869A (en) * | 2016-04-08 | 2017-10-20 | 财团法人纺织产业综合研究所 | Polyimide composition and method for producing separation membrane |
| CN111073283A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
-
2022
- 2022-03-14 CN CN202210244950.3A patent/CN114702671A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728697A (en) * | 1985-09-27 | 1988-03-01 | General Electric Company | Novel copolyamideimides, prepolymers therefor and method for their preparation |
| CN107261869A (en) * | 2016-04-08 | 2017-10-20 | 财团法人纺织产业综合研究所 | Polyimide composition and method for producing separation membrane |
| CN111073283A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 唐传林: "《绝缘材料工艺原理》", 机械工业出版社, pages: 210 - 214 * |
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