CN113150278A - Polyimide containing asymmetric indole structure and preparation method thereof - Google Patents
Polyimide containing asymmetric indole structure and preparation method thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 114
- 239000004642 Polyimide Substances 0.000 title claims abstract description 113
- 125000001041 indolyl group Chemical group 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 150000004985 diamines Chemical class 0.000 claims abstract description 48
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 29
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 15
- IEBQZJXMAOMNBO-UHFFFAOYSA-N 1h-indole;pyridine Chemical compound C1=CC=NC=C1.C1=CC=C2NC=CC2=C1 IEBQZJXMAOMNBO-UHFFFAOYSA-N 0.000 claims abstract description 8
- FMSSKCBYHCEFQE-UHFFFAOYSA-N 1h-indole;pyrimidine Chemical compound C1=CN=CN=C1.C1=CC=C2NC=CC2=C1 FMSSKCBYHCEFQE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 63
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 8
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 8
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 7
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
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- 238000001914 filtration Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 4
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 19
- -1 pyrimidine indole diamine Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010907 mechanical stirring Methods 0.000 description 12
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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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
-
- 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
-
- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to polyimide containing an asymmetric indole structure and a preparation method thereof. The structure of the polyimide containing the asymmetric indole structure comprises any one of the following general formulas:
wherein n is a positive integer of 1 or more; the preparation method comprises the following steps: dissolving a pyrimidine indole type diamine monomer or pyridine indole type diamine monomer in a first solvent to obtain a diamine monomer solution; mixing the diamine monomer solution with dianhydride to carry out a first reaction to obtain a polyamic acid solution; mixing anhydride and pyridine to obtain a first solution; mixing the polyamic acid solution with the first solution to perform a second reactionAnd obtaining a second solution. The raw materials of the invention are diamine monomers (DAPPI and DAPPDI), the source is wide, and the processability is excellent; the prepared polyimide has good high temperature resistance and excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to polyimide containing an asymmetric indole structure and a preparation method thereof.
Background
Polyimide (PI) is an organic polymer material containing imide rings in a molecular structure. The rigid imide ring endows the material with excellent comprehensive performance, such as excellent thermal stability, excellent mechanical performance, outstanding chemical and radiation resistance, excellent dielectric performance and the like. Due to its unique properties, polyimide has received a high degree of attention, and is widely used as an insulating material, a waveguide material, a high-mode fiber, a selectively permeable film, a high-temperature composite material, and the like, and relates to various fields such as aerospace, chemical engineering, electrical appliances, microelectronics, and the like. In recent years, polyimide has been considered by researchers to be the most promising polymer material in the future, and countries are researching, developing and utilizing polyimide as one of the most promising engineering plastics listed in the 21 st century.
However, the main chain of the polyimide molecule generally contains benzene ring and imide ring structure, and the polyimide has strong intermolecular action due to electron polarization and crystallinity, resulting in close packing of polyimide molecular chains, so that the polyimide mainly has the following disadvantages: (1) most conventional polyimides are difficult to process because they are poorly soluble or insoluble in common solvents, and therefore the polyimides are usually synthesized in a two-step process: the first step is dianhydride and diamine in polar aprotic reaction solvent to form polyamic acid (PAA); the second step is the imidization of hot PAA to polyimide. (2) The traditional polyimide has higher melting temperature due to the characteristic of a rigid chain, and is not easy to process and form, which causes great difficulty for practical production and application; (3) the film made of traditional polyimide is generally hard and brittle, and has insufficient strength, and the defect that the linear expansion coefficient and the mechanical strength are difficult to be considered when the film is used in the microelectronic industry. Meanwhile, the raw materials are expensive, so that the preparation cost of the polyimide is always high. In view of the above disadvantages of polyimide, it is necessary to research the modification of the molecular structure of polyimide and the optimization of the polyimide synthesis process to continuously meet the performance requirements of new products.
At present, in the process of developing a polyimide substitute, a polyimide with good high temperature resistance and excellent mechanical properties is urgently needed, and meanwhile, the raw material cost is urgently needed to be reduced, and the processability of the raw material is needed to be improved.
Disclosure of Invention
In view of the above problems, the present invention provides a polyimide containing an asymmetric indole structure and a method for preparing the same to overcome the above problems or at least partially solve the above problems.
The technical scheme for realizing the purpose is as follows:
the invention provides polyimide containing an asymmetric indole structure, wherein the structure of the polyimide containing the asymmetric indole structure comprises any one of the following general formulas:
The invention also provides a preparation method of the polyimide containing the asymmetric indole structure, which comprises the following steps:
dissolving a pyrimidine indole type diamine monomer or pyridine indole type diamine monomer in a first solvent to obtain a diamine monomer solution;
mixing the diamine monomer solution with dianhydride to carry out a first reaction to obtain a polyamic acid solution;
mixing anhydride and pyridine to obtain a first solution, or mixing anhydride and triethylamine to obtain a first solution;
and mixing the polyamic acid solution with the first solution, and carrying out a second reaction to obtain a second solution.
Optionally, the pyrimidine indole diamine monomer comprises 5-amino-2- (3-aminophenyl) -N-pyrimidine indole (DAPPI), and the pyridine indole diamine monomer comprises 5-amino-2- (3-aminophenyl) -N-pyridine indole (DAPPI).
2. Alternatively, the dianhydride comprises any one of 3,3',4,4' -biphenyltetracarboxylic dianhydride, bisphenol a type diether dianhydride (BPADA), 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), and 4,4' -oxydiphthalic anhydride (ODPA), and the first solvent comprises any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide.
Optionally, the reaction conditions of the first reaction are: reacting for 10-16 h at room temperature in a protective gas environment.
Optionally, the anhydride comprises acetic anhydride, and the volume ratio of the acetic anhydride to the pyridine is 1-3: 1.
Optionally, the reaction conditions of the second reaction include: the temperature is 80-110 ℃ and the reaction is carried out for 4-12 h in a violent stirring reflux environment.
Optionally, the preparation method further comprises the following steps:
cooling the second solution, and mixing the cooled second solution with an alcoholic solution to obtain a precipitated solid;
carrying out suction filtration and/or drying on the precipitated solid, and dissolving the precipitated solid in a second solvent to obtain a third solution;
and coating the third solution to form a film, and carrying out temperature programming to obtain the polyimide containing the asymmetric indole structure.
Optionally, the alcohol solution is a methanol solution; the step of filtering and/or drying the precipitated solid comprises the following steps: and carrying out suction filtration on the precipitated solid, and drying at the temperature of 160-200 ℃ for 20-26 h after suction filtration.
Optionally, the second solvent comprises any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages: the polyimide containing the asymmetric indole structure has good high temperature resistance; under the nitrogen atmosphere, the 5 percent thermal weight loss temperature is 504.8-516.4 ℃, and the carbon residue rate is more than 60 percent at 800 ℃; the elongation at break is between 5.6 and 18.5 percent, the tensile modulus is between 13.5 and 16.1GPa, and the composite material has excellent mechanical properties; the polyimide containing the asymmetric indole structure is easy to dissolve in a solvent and convenient to process, and is light yellow.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic diagram of a process for synthesizing polyimide containing asymmetric indole structure by using DAPPI as a pyrimidine indole diamine monomer and dianhydride;
FIG. 2 is a schematic diagram of a process for synthesizing polyimide containing an asymmetric indole structure by using DAPPDI as a pyridine indole diamine monomer and dianhydride;
FIG. 3 is an infrared spectrum of a polyimide containing an asymmetric indole structure synthesized by using DAPPI and DAPPDI as diamine monomers and dianhydride in an example;
FIG. 4 is the X-ray diffractometer (XRD) graph of polyimide containing asymmetric indole structure synthesized by using DAPPI and DAPPDI as diamine monomers and dianhydride in the example;
FIG. 5 is a graph of static thermomechanical analyzer (TMA) of polyimide containing asymmetric indole structure synthesized with diamine monomers and dianhydride using DAPPI and DAPPDI in the examples;
FIG. 6 is a thermogravimetric analyzer (TG) graph of polyimide containing asymmetric indole structure synthesized by using DAPPI and DAPPDI as diamine monomers and dianhydride in the example;
FIG. 7 is a graph of mechanical properties of polyimides containing asymmetric indole structures synthesized in examples using DAPPI and DAPPDI as diamine monomers and dianhydrides.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
It should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present invention, "first solvent", "second solvent", "first reaction", "second reaction", "first solution", "second solution", and "third solution" do not refer to a sequential relationship, and are used merely as terms for distinction.
Herein, "dianhydride" is intended to include precursors or derivatives thereof, which technically may not be a dianhydride, but which nevertheless react with a diamine to form a polyamic acid which can be reconverted to a polyimide containing an asymmetric indole structure.
Herein "pyrimidine indole diamine monomer", "pyridine indole diamine monomer" are intended to include precursors or derivatives thereof, which technically may not be a diamine, but nevertheless will react with a dianhydride to form a polyamic acid which can be reconverted to a polyimide containing an asymmetric indole structure.
In order to solve the technical problems, the technical scheme in the embodiment of the invention has the following general idea:
according to an exemplary embodiment of the present invention, there is provided an asymmetric indole structure-containing polyimide, wherein the structure of the asymmetric indole structure-containing polyimide includes any one of the following general formulas:
wherein n is a positive integer of 1 or more. Optionally, n is any one of 1, 2, 3 and 4.
The polyimide synthesized by the invention can be amorphous powder or film, is convenient for storage and transportation, and is beneficial to the reprocessing of polyimide materials. The polyimide containing the asymmetric indole structure has good high temperature resistance; under the nitrogen atmosphere, the 5 percent thermal weight loss temperature is 504.8-516.4 ℃, and the carbon residue rate is more than 60 percent at 800 ℃; the elongation at break is between 5.6 and 18.5 percent, the tensile modulus is between 13.5 and 16.1GPa, and the composite material has excellent mechanical properties; easy to dissolve in solvent and easy to process.
The invention also provides a preparation method of the polyimide containing the asymmetric indole structure, which comprises the following steps:
dissolving a pyrimidine indole type diamine monomer or pyridine indole type diamine monomer in a first solvent to obtain a diamine monomer solution;
the preparation method adopts a pyrimidine indole type diamine monomer or pyridine indole type diamine monomer as a raw material, adopts two novel diamine monomers (DAPPI and DAPPDI) containing asymmetric indole structures, has a novel structure, and greatly reduces the cost of the raw material and the process compared with the traditional process; meanwhile, the diamine monomer is easy to dissolve in the first solvent, so that the chemical reaction is convenient to carry out.
Mixing the diamine monomer solution with dianhydride to carry out a first reaction to obtain a polyamic acid solution; mixing anhydride and pyridine to obtain a first solution, or mixing anhydride and triethylamine to obtain a first solution;
and mixing the polyamic acid solution with the first solution, and carrying out a second reaction to obtain a second solution.
The diamine monomer solution and the dianhydride are mixed with the polyamic acid solution and the first solution, the molar ratio and the mass ratio of the diamine monomer solution and the dianhydride are not specifically required, only the corresponding polyamic acid and the polyimide containing the asymmetric indole structure need to be generated, and the amount of the polyimide containing the asymmetric indole structure possibly generated is small as long as the polyimide containing the asymmetric indole structure can be generated.
The polyamic acid solution in the second solution has undergone dehydration reaction to produce a part of the polyimide containing an asymmetric indole structure of the present invention, but the dehydration reaction is not complete enough. The polyimide containing the asymmetric indole structure solves the problem of close packing of the molecular chains of the traditional polyimide, has excellent thermal stability, is easy to dissolve in a solvent, and has good processing performance.
In an alternative embodiment, the pyrimidineindole diamine monomer is 5-amino-2- (3-aminophenyl) -N-pyrimidineindole (DAPPI) and the pyridine indole diamine monomer is 5-amino-2- (3-aminophenyl) -N-pyridoindole (DAPPI). The DAPPI has the performance of a pyrimidine indole type diamine monomer, can be used as a raw material of polyimide with an asymmetric indole structure, the DAPPDI has the performance of a pyridine indole type diamine monomer, and can be used as a raw material of polyimide with an asymmetric indole structure, the DAPPI and the DAPPDI are two raw materials with novel structures and low cost, and are used for synthesizing the polyimide with the asymmetric indole structure.
As an alternative embodiment, the dianhydride includes any one of 3,3',4,4' -biphenyltetracarboxylic dianhydride, bisphenol a type diether dianhydride (BPADA), 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), and 4,4' -oxydiphthalic anhydride (ODPA), and the first solvent includes any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide. The 3,3',4,4' -biphenyl tetracarboxylic dianhydride is an asymmetric structural monomer, is suitable for producing high-temperature-resistant composite materials, and can react with the diamine monomer to obtain a polyamic acid solution; the pyrimidine indole diamine monomer or pyridine indole diamine monomer can be dissolved in a solvent such as N, N-dimethylacetamide, and N, N-dimethylacetamide can be distilled and separated at normal pressure because it is not decomposed by heating to boiling at normal pressure in the absence of an acid or a base.
As an alternative embodiment, the reaction conditions of the first reaction are: reacting for 10-16 h at room temperature in a protective gas environment. The first reaction can be smoothly carried out by selecting the room temperature condition, so that the operation of personnel is convenient, and the production cost is saved. Considering that the amido in some diamine monomers is more active, is easy to oxidize in the air and has higher toxicity, and the reaction in a protective gas environment is convenient to isolate the toxicity. The reaction time is controlled to be 10-16 h, more uniform and viscous light yellow transparent polyamic acid can be conveniently obtained, and if the reaction time is too short, the amount of the polyamic acid obtained by the reaction is too small; if the reaction time is too long, it may cause the monomers and the substances in the solution to absorb water.
In an alternative embodiment, the acid anhydride comprises acetic anhydride, and the volume ratio of the acetic anhydride to the pyridine is 1 to 3: 1. The volume ratio of the acetic anhydride to the pyridine is more than one, the dehydration rate is higher when the volume ratio is 1-3: 1, and reaction reagents are saved; the dehydration reaction can also be carried out when the volume ratio of the acetic anhydride to the pyridine is less than one, but the reaction speed and the dehydration efficiency are low, so that the dehydration of the polyamic acid is incomplete.
As an alternative embodiment, the reaction conditions of the second reaction include: the temperature is 80-110 ℃ and the reaction is carried out for 4-12 h in a violent stirring reflux environment. The reaction rate is high at the temperature of 80-110 ℃, the dehydration of the polyamic acid can be promoted under the condition of violent stirring and refluxing, and the reaction can be completed in the conventional stirring and refluxing condition for 4-12 h.
As an alternative embodiment, the preparation method further comprises the following steps:
cooling the second solution, and mixing the cooled second solution with an alcoholic solution to obtain a precipitated solid; carrying out suction filtration and/or drying on the precipitated solid, and dissolving the precipitated solid in a second solvent to obtain a third solution; and coating the third solution to form a film, and carrying out temperature programming to obtain the polyimide containing the asymmetric indole structure.
The polyamic acid solution in the second solution has undergone dehydration reaction to produce a part of the polyimide containing an asymmetric indole structure of the present invention, but the dehydration reaction is not complete enough. In order to completely shrink the polyamic acid to obtain more polyimide containing the asymmetric indole structure, the polyimide containing the asymmetric indole structure and the polyamic acid are subjected to suction filtration and/or drying operation to be purified; the purified solid can not be directly dehydrated, and the solid needs to be dissolved in a solvent, then knife coating and film forming and temperature programming are carried out, and the polyimide containing the asymmetric indole structure with high proportion is obtained after complete shrinkage.
The temperature programming is to perform gradient temperature raising on the polyamic acid, so that the polyamic acid can be quickly and effectively subjected to dehydration reaction, less impurities are generated, and high yield of the polyimide containing the asymmetric indole structure is realized.
Compared with the traditional aromatic polyimide, the amorphous aggregated structure polyimide film prepared from the polyimide containing the asymmetric indole structure provided by the embodiment of the invention has obviously improved processing performance: the traditional polyimide is difficult to process because of being difficult to dissolve or insoluble in common solvents, and the processing needs higher melting temperature, and the polyimide containing the asymmetric indole structure is easy to dissolve in the solvents and can be reacted at room temperature and lower temperature.
As an alternative embodiment, the alcohol solution is a methanol solution; the step of filtering and/or drying the precipitated solid comprises the following steps: and carrying out suction filtration on the precipitated solid, and drying at the temperature of 160-200 ℃ for 20-26 h after suction filtration.
The precipitated solid is preferably filtered with suction and/or dried to remove a solvent such as methanol, ethanol, or water.
As an alternative embodiment, the second solvent includes any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide. The polyimide containing the asymmetric indole structure can be dissolved in N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide, and the N, N-dimethylacetamide can be heated to boiling without decomposition under normal pressure in the absence of acid and alkali, so that the polyimide can be distilled and separated under normal pressure.
The polyimide having an asymmetric indole structure of the present invention will be described in detail below with reference to examples and experimental data.
Example 1
(1) Cleaning all glass instruments used in the experiment, drying for later use, adding (4.0mmol,1.205g) DAPPI, N, N-dimethylacetamide (DMAc)6.0362mL into a 100mL three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving diamine monomers in the DMAc under the condition of mechanical stirring, adding 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) (4.0mmol,1.177g) in batches, and reacting for 14 hours after complete dissolution to obtain 15% of solid content;
(2) a homogeneous and viscous, light yellow transparent polyamic acid was obtained, acetic anhydride was added: placing the mixed solution of 2:1 pyridine at 100 ℃ and stirring and refluxing for 4h vigorously;
(3) after cooling, dropping the reaction liquid into a methanol solution, separating out a solid, performing suction filtration, and drying the obtained solid in a vacuum oven at 180 ℃ for 24 hours to obtain polyimide powder;
(4) dissolving a proper amount of powder in N, N-dimethylacetamide, coating by a scraper to form a film, and carrying out temperature programming to obtain the polyimide.
Example 2
(1) Cleaning all glass instruments used in the experiment, drying for later use, adding (4.0mmol,1.201g) of DAPPDI, N, N-dimethylacetamide (DMAc)10.2660mL into a 100mL three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving diamine monomers in DMAc under the condition of mechanical stirring, adding 3,3',4,4' -biphenyltetracarboxylic dianhydride (4.0mmol,1.177g) in batches, and reacting for 14h after complete dissolution to obtain a solid content of 10%;
(2) a homogeneous and viscous, light yellow transparent polyamic acid was obtained, acetic anhydride was added: placing the mixed solution of 2:1 pyridine at 100 ℃ and stirring and refluxing for 6h vigorously;
(3) after cooling, dropping the reaction liquid into a methanol solution, separating out a solid, performing suction filtration, and drying the obtained solid in a vacuum oven at 180 ℃ for 24 hours to obtain polyimide powder;
(4) and dissolving a proper amount of powder in a second solvent, coating the solution by a scraper to form a film, and carrying out temperature programming to obtain the polyimide. The second solvent comprises any one of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide.
Example 3
(1) Cleaning all glass instruments used in the experiment, drying for later use, adding (4.0mmol,1.205g) pyrimidine indole type diamine monomer (DAPPI) and 8.0362mL into a 100mL three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving the diamine monomer in DMAc under the condition of mechanical stirring, adding 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA) (6.0mmol,1.766g) in batches, and reacting for 10 hours after complete dissolution;
(2) a homogeneous and viscous, light yellow transparent polyamic acid was obtained, acetic anhydride was added: mixed solution of pyridine 1:1, placed under vigorous stirring and reflux at 110 ℃ for 12 h.
Example 4
(1) Cleaning all glass instruments used in the experiment, drying for later use, adding (6.0mmol,1.808g) pyridine indole type diamine monomer (DAPPDI) and 6.0362mL dimethyl sulfoxide into a 100mL three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving the diamine monomer in a solvent under the condition of mechanical stirring, adding 4,4' -oxydiphthalic anhydride (4.0 mmol) in batches, and reacting for 16h after complete dissolution;
(2) to obtain uniform and viscous pale yellow transparent polyamic acid, a mixed solution of acid anhydride and triethylamine was added, and the mixture was stirred vigorously at 80 ℃ and refluxed for 7 hours.
Example 5
(1) Cleaning all glass instruments used in the experiment, drying for later use, adding pyridine indole diamine monomer (DAPPI) and N-methylpyrrolidone into a three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving the diamine monomer in a solvent under the condition of mechanical stirring, adding 3,3', 4' -benzophenone tetracarboxylic dianhydride, and reacting after complete dissolution;
(2) a homogeneous and viscous, light yellow transparent polyamic acid was obtained, acetic anhydride was added: pyridine is mixed with 2.6:1, and the mixture is reacted.
Example 6
(1) Completely cleaning glass instruments used in an experiment, drying the glass instruments for later use, adding pyridine indole diamine monomer (DAPPDI) and N, N-dimethylformamide into a three-neck flask provided with a mechanical stirring rod and a nitrogen protection device, uniformly dissolving the diamine monomer into the N, N-dimethylformamide under the condition of mechanical stirring, then adding bisphenol A diether dianhydride, and reacting after complete dissolution;
(2) a homogeneous and viscous, light yellow transparent polyamic acid was obtained, acetic anhydride was added: pyridine is mixed with 2.6:1, and the mixture is reacted.
The polyimide containing the asymmetric indole structure synthesized in the example was tested:
the thermal stability of the polyimide is measured by adopting a TG209F3 thermogravimetric analyzer produced by Germany Netzsch company, wherein the heating rate is 20 ℃/min and the temperature range is 40-800 ℃ under the nitrogen atmosphere; the glass transition temperature of the material was measured using a model Q400 static thermodynamic analyzer manufactured by TA instruments of America, with a static force set at 0.05N, with a flow of 50mL/min under a nitrogen atmosphere and a temperature rise rate of 20 ℃/min. The polyimide testing temperature is obtained at 40-400 ℃, a film stretching mode is set, two times of heating treatment are carried out in the testing process, and the testing result is obtained from heating data of the sample after the heat history is removed by annealing; the mechanical properties of the polymer are tested by adopting an IBTC-300S type micro in-situ mechanical test system produced by Kaire test and control system (Tianjin) Co.
Table 1 thermal properties of polyimides containing asymmetric indole structures.
Table 1 shows the thermogravimetric data of the polyimides of examples 1 to 2; the polyimide synthesized by the embodiment of the invention is at 504.8-516.4 ℃ under the nitrogen atmosphere when the weight loss is 5%; when the weight loss is 10%, the temperature is 573.2-574.1 ℃, and the high temperature resistance is good; at 800 ℃, the carbon residue rate is more than 60 percent; in conclusion, the polyimide containing the asymmetric indole structure synthesized by the invention has excellent thermal stability.
Table 2 mechanical properties of polyimides containing asymmetric indole structures.
Table 2 shows the mechanical test data of the polyimides obtained in examples 1 and 2, wherein the polyimides have tensile strength of 84.8MPa to 116.4MPa, elongation at break of 5.6% to 18.5%, and tensile modulus of 13.5 GPa to 16.1GPa, and in conclusion, the polyimides containing asymmetric indole structures have excellent mechanical properties.
Description of the attached drawings 1-3:
FIG. 1 is a schematic diagram of a process for synthesizing polyimide containing asymmetric indole structure by using DAPPI as a pyrimidine indole diamine monomer and dianhydride; FIG. 2 is a schematic diagram of a process for synthesizing polyimide containing an asymmetric indole structure by using DAPPDI as a pyridine indole diamine monomer and dianhydride; the DAPPI and the DAPPDI are two raw materials with novel structures and low cost, are used for synthesizing polyimide containing an asymmetric indole structure, and have greatly reduced process cost compared with the traditional process; meanwhile, the diamine monomer is easy to dissolve in the first solvent, so that the chemical reaction is convenient to carry out. The polyimide and dianhydride are synthesized to obtain uniform and viscous light yellow transparent polyamic acid under the action of various catalysts, and dehydration reaction can be carried out in various ways to obtain polyimide containing an asymmetric indole structure, and the polyimide has more beneficial high-temperature performance, mechanical performance and processing performance than the traditional polyimide.
The infrared spectrogram of polyimide synthesized by using 5-amino-2- (3-aminophenyl) -N-pyrimidine indole and 5-amino-2- (3-aminophenyl) -N-pyridine indole as diamine monomers and dianhydride is shown in figure 3, and the X-ray diffraction spectrum is shown in figure 4, so that the structure of the polyimide containing the asymmetric indole structure is determined; the graph of a static thermomechanical analyzer (TMA) of the polyimide containing the asymmetric indole structure is shown in figure 5, and the deformation quantity of the polyimide containing the asymmetric indole structure is determined as a function of temperature and time at a program temperature; a thermogravimetric analysis (TGA) graph of the polyimide containing the asymmetric indole structure is shown in figure 6, and the function relationship between the mass variation of the polyimide containing the asymmetric indole structure and the corresponding temperature is determined; the mechanical property curve chart of the amine of the polyimide containing the asymmetric indole structure is shown in figure 7, and the functional relationship between the stress and the corresponding strain of the polyimide containing the asymmetric indole structure is determined; the physical and chemical properties of the polyimide containing the asymmetric indole structure are analyzed from various angles, and the method is convenient for wide popularization and application.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The polyimide containing the asymmetric indole structure is characterized in that the structure of the polyimide containing the asymmetric indole structure comprises any one of the following general formulas:
wherein n is a positive integer of 1 or more.
2. The preparation method of the polyimide containing the asymmetric indole structure according to claim 1, wherein the preparation method comprises the following steps:
dissolving a pyrimidine indole type diamine monomer or pyridine indole type diamine monomer in a first solvent to obtain a diamine monomer solution;
mixing the diamine monomer solution with dianhydride to carry out a first reaction to obtain a polyamic acid solution;
mixing anhydride and pyridine to obtain a first solution, or mixing anhydride and triethylamine to obtain a first solution;
and mixing the polyamic acid solution with the first solution, and carrying out a second reaction to obtain a second solution.
3. The method for preparing polyimide containing asymmetric indole structure according to claim 2, wherein the pyrimidine indole type diamine monomer comprises 5-amino-2- (3-aminophenyl) -N-pyrimidine indole, and the pyridine indole type diamine monomer comprises 5-amino-2- (3-aminophenyl) -N-pyridine indole.
4. The method for preparing polyimide having an asymmetric indole structure according to claim 2, wherein the dianhydride comprises any one of 3,3',4,4' -biphenyltetracarboxylic dianhydride, bisphenol a type diether dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, and 4,4' -oxydiphthalic anhydride, and the first solvent comprises any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide.
5. The method for preparing polyimide containing an asymmetric indole structure according to claim 2, wherein the reaction conditions of the first reaction are as follows: reacting for 10-16 h at room temperature in a protective gas environment.
6. The method for preparing polyimide containing an asymmetric indole structure according to claim 2, wherein the acid anhydride comprises acetic anhydride, and the volume ratio of the acetic anhydride to the pyridine is 1-3: 1.
7. The method for preparing polyimide containing an asymmetric indole structure according to claim 2, wherein the reaction conditions of the second reaction include: the temperature is 80-110 ℃ and the reaction is carried out for 4-12 h in a violent stirring reflux environment.
8. The method for preparing polyimide containing an asymmetric indole structure according to any one of claims 2 to 7, wherein the method further comprises the following steps:
cooling the second solution, and mixing the cooled second solution with an alcoholic solution to obtain a precipitated solid;
carrying out suction filtration and/or drying on the precipitated solid, and dissolving the precipitated solid in a second solvent to obtain a third solution;
and coating the third solution to form a film, and carrying out temperature programming to obtain the polyimide containing the asymmetric indole structure.
9. The method for preparing polyimide containing an asymmetric indole structure according to claim 8, wherein the alcohol solution is any one of a methanol solution, ethanol, water, a mixed solution of methanol and water, and a mixed solution of ethanol and water; the step of filtering and/or drying the precipitated solid comprises the following steps: and carrying out suction filtration on the precipitated solid, and drying at the temperature of 160-200 ℃ for 20-26 h after suction filtration.
10. The method for preparing polyimide containing an asymmetric indole structure according to claim 8, wherein the second solvent comprises any one of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide.
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