CN107056711B - Diamine monomer containing pyridazine group and preparation method and application thereof - Google Patents
Diamine monomer containing pyridazine group and preparation method and application thereof Download PDFInfo
- Publication number
- CN107056711B CN107056711B CN201710328488.4A CN201710328488A CN107056711B CN 107056711 B CN107056711 B CN 107056711B CN 201710328488 A CN201710328488 A CN 201710328488A CN 107056711 B CN107056711 B CN 107056711B
- Authority
- CN
- China
- Prior art keywords
- diamine monomer
- pyridazinoxy
- hours
- amino
- pyridazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/22—Nitrogen and oxygen atoms
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to a pyridazine group-containing diamine monomer and a preparation method and application thereof, belonging to the technical field of organic synthesis. The invention provides a diamine monomer containing a pyridazine structure as well as a preparation method and application thereof, wherein a nucleophilic substitution method is adopted to react a dihydroxy compound containing a flexible group, an asymmetric structure or a large-volume side group with chloronitropyridazine to prepare a dinitro intermediate containing the pyridazine structure, and the dinitro product intermediate containing the pyridazine structure is reduced to obtain the diamine monomer containing the pyridazine structure; and (2) reacting a diamine monomer containing a pyridazine structure with dianhydride, and performing thermal imidization to obtain the high-performance heterocyclic polyimide film. The high-performance heterocyclic polyimide film disclosed by the invention not only keeps the excellent thermal property and mechanical property of the original polyimide, but also remarkably improves the solubility and light transmittance, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a diamine monomer containing a pyridazine structure and a preparation method and application thereof.
Background
Polyimide is an aromatic heterocyclic polymer material with an imide ring repeating unit on a molecular main chain. The unique aromatic structure endows the polyimide with excellent high temperature resistance, outstanding mechanical property, optical property, aging resistance, radiation resistance and solvent resistance, and enables the polyimide to have longer service life and higher safety factor, thereby being widely applied to the fields of coatings, adhesives, aerospace, automobiles, electronics and electricity and the like, in particular to the high-end technical field, such as the fields of aerospace and microelectronics, and being one of indispensable materials.
Although the unique structure of polyimide endows polyimide with various excellent properties, the polyimide still has some problems, on one hand, the polyimide has more aromatic ring structures on the main chain, so that the polyimide has higher rigidity and is difficult to dissolve in an organic solvent or has higher melting temperature, so that the polyimide is difficult to mold and process, and the development of the polyimide is limited; on the other hand, the transparency of polyimide is deteriorated by an electron polarization effect and a Charge Transfer Complex (CTC) effect. Meanwhile, polyimide molecular chains have strong interaction, so that charge transfer complexes among the molecular chains are caused, and the polyimide has dark color. In order to meet the requirements of the rapidly developing fields of microelectronics, optical applications and the like, such as a flexible substrate and a thin-film solar cell substrate adopted by a flexible display technology, the preparation of a polyimide material which is easy to process, high in solubility and high in optical transmittance is very important.
Disclosure of Invention
The invention aims to solve the technical problem of poor optical transmittance of polyimide materials. In order to solve the problem, the invention provides a diamine monomer containing a pyridazine structure, and a preparation method and application thereof.
The technical scheme adopted by the invention is that a nucleophilic substitution method is adopted to react a dihydroxy compound containing a flexible group, an asymmetric structure or a bulky side group with chloronitropyridazine to prepare a dinitro intermediate containing a pyridazine structure, and the dinitro product intermediate containing the pyridazine structure is reduced to obtain a diamine monomer containing the pyridazine structure; the diamine monomer containing pyridazine structure reacts with dianhydride to obtain the high-performance heterocyclic polyimide film with the advantages of high thermal stability, mechanical strength, high optical permeability and the like.
The invention adopts the specific technical scheme that a diamine monomer containing a pyridazine structure has a structural formulawherein-Ar-is preferably
One kind of (1).
The reaction formula for preparing the diamine monomer containing the pyridazine structure is as follows:
A preparation method of a diamine monomer containing a pyridazine structure comprises the following steps:
(1) under the conditions of room temperature and nitrogen protection, dissolving a dihydroxy compound, 3-chloro-2-nitropyridazine and alkali in a polar solvent, wherein the total mass fraction of solids in the system is 10-50%, heating to 50-100 ℃, and reacting for 4-8 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, and repeatedly washing the obtained solid with deionized water until the washing liquid is neutral to obtain a crude dinitro product; dissolving the dinitro crude product and activated carbon in an organic solvent 1, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 50-100 ℃ for 5-10 hours to obtain a dinitro intermediate containing a pyridazine structure;
(2) under the protection of nitrogen, adding a dinitro intermediate product containing a pyridazine structure into an organic solvent 2, adding a catalyst, slowly dropwise adding hydrazine hydrate at the temperature of 60-80 ℃ at the speed of 20-30 mL/h, continuously reacting for 2-3 hours after dropwise adding is finished within 1.5-2 hours, carrying out hot filtration, cooling filtrate to separate out a solid, filtering, washing a filter cake with distilled water for 2-3 times, and carrying out vacuum treatment at the temperature of 50-100 ℃ for 5-10 hours to obtain a diamine monomer containing the pyridazine structure;
the molar ratio of the dihydroxy compound, the 3-chloro-2-nitropyridazine, the alkali and the polar solvent is 1: 2.4-3: 29.6-35.5; the mass ratio of the dinitro crude product to the organic solvent 1 to the active carbon is 1: 5-8: 0.4-0.6; the mass ratio of the dinitro intermediate product containing a pyridazine structure to the catalyst to the hydrazine hydrate is 1: 0.5-0.8: 3-5; the dihydroxy compound is preferably one of 3-hydroxy-6- (4-hydroxyphenoxy) biphenyl, 4 ' -dihydroxydiphenylmethane, 3 ' -dihydroxydiphenylmethane, 1, 4-bis (3-hydroxyphenoxy) benzene, 1- (3-hydroxyphenoxy) -4- (4 ' -hydroxyphenoxy) benzene, biphenol, hydroquinone, resorcinol and hexafluorobisphenol A; the polar solvent is preferably one of N, N '-dimethylacetamide, N' -dimethylformamide and N-methylpyrrolidone; the alkali is preferably one of potassium hydroxide, potassium carbonate and sodium carbonate; the organic solvent 1 is preferably one of N, N '-dimethylacetamide, N' -dimethylformamide and N-methylpyrrolidone; the organic solvent 2 is preferably one of tetrahydrofuran, dioxane and ethanol; the catalyst is preferably one of palladium carbon, nickel carbon, platinum carbon and raney nickel.
The application of a diamine monomer containing a pyridazine structure comprises the step of polymerizing the diamine monomer containing the pyridazine structure with dianhydride to obtain high-performance heterocyclic polyimide, wherein the structural formula of the high-performance heterocyclic polyimide is as follows:
The application of the diamine monomer containing the pyridazine structure comprises the following preparation process of a high-performance heterocyclic polyimide film:
(1) under the conditions of room temperature and nitrogen protection, dissolving a diamine monomer containing a pyridazine structure in a polar solvent, after completely dissolving, slowly adding dianhydride, and stirring for 12 hours to obtain a polyamic acid solution;
(2) pouring the polyamic acid solution onto a clean glass plate, leveling the polyamic acid solution with a scraper, and putting the glass plate into a program oven to remove a solvent and imidize the polyamic acid solution; the temperature-raising program is as follows: 5 hours at 60 ℃; at 80 ℃ for 2 hours; 2 hours at 100 ℃; 1 hour at 12 ℃; 200 ℃, 1 hour, 250 ℃, 1 hour; at 280 ℃ for 1 hour; cooling to room temperature after imidization is finished, putting the glass plate into deionized water for demoulding to obtain an imidized film, and drying at 60 ℃ for 12 hours to obtain a high-performance heterocyclic polyimide film;
the molar ratio of diamine monomer containing pyridazine structure, dianhydride and polar solvent is 1:1: 10-12; the diamine monomer having a pyridazine structure is preferably 3- (6-amino-3-pyridazinoxy) -6- [4- (6-amino-3-pyridazinoxy) phenoxy ] biphenyl, 1, 3-bis (6-amino-3-pyridazinoxy) benzene, 1, 4-bis (6-amino-3-pyridazinoxy) benzene, 4 '-bis (6-amino-3-pyridazinoxy) biphenyl, 2' -bis [ (6-amino-3-pyridazinoxy) benzene ] hexafluoropropane, 4 '-bis (6-amino-3-pyridazinoxy) diphenylmethane, 3' -bis (6-amino-3-pyridazinoxy) diphenylmethane, one of 1- [3- (6-amino-3-pyridazinyloxy) phenoxy ] -4- [ 4' - (6-amino-3-pyridazinyloxy) phenoxy ] benzene and 1, 4-bis [3- (6-amino-3-pyridazinyloxy) ] benzene; the dianhydride is preferably one of pyromellitic anhydride, 3,3 ', 4, 4' -benzophenone tetracarboxylic anhydride, 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, 4, 4' -oxydiphthalic anhydride, 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic anhydride, 3,3 ', 4, 4' -biphenyl tetracarboxylic anhydride, 4,4 '- (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride), 2,3,3 ', 4' -biphenyl tetracarboxylic anhydride and hydrogenated pyromellitic anhydride; the polar solvent is preferably one of N, N '-dimethylacetamide, N' -dimethylformamide and N-methylpyrrolidone.
-Ar' -preferably
One kind of (1).
The invention designs and synthesizes a diamine monomer from the aspects of molecular design and practical application. The diamine monomer is used as a raw material, and is polymerized with commercial dianhydride at normal temperature to obtain polyamic acid, and then the polyamic acid is subjected to thermal imidization to obtain the polyimide film containing the pyridazine structure, so that the film not only keeps the excellent thermal property and mechanical property of the original polyimide, but also is remarkably improved in the aspects of solubility and light transmittance.
Compared with the prior art, the invention has the beneficial effects that:
(1) from the angle of molecular design and practical application, in order to reduce the interaction force among molecules, a flexible structure is introduced into a main chain of a diamine monomer, or the main chain adopts an asymmetric structure, or a bulky side group is introduced into the main chain, so that the rigidity of the molecular chain can be effectively reduced, the flow of charges along the molecular chain direction is hindered, the conjugation among the molecular chains and the formation of a Charge Transfer Complex (CTC) are reduced, the polyimide is changed from dark brown to light yellow, and the optical transmission performance of the polyimide is enhanced; meanwhile, the pyridazine structure is introduced into the main chain because the rigidity of the main chain is stronger than that of a benzene ring due to the structural characteristics of the pyridazine structure, the heat resistance and the chemical resistance of the polymer can be effectively improved by introducing the pyridazine structure, the loss in the aspects of heat and chemical resistance caused by the introduction of a flexible bond is made up to a certain extent, and meanwhile, experiments prove that the pyridazine structure has certain contribution to the optical transmittance of polyimide.
(2) The synthetic technical route has reasonable and definite design, simple operation and low cost; the synthesis reaction temperature is low, and the Pd/C and hydrazine hydrate system is used for reduction, thereby avoiding adopting H2Harsh conditions for reduction, and avoids using SnCl2After the system is reducedThe handling is difficult. The obtained product has high purity and simple post-treatment. The yield of the finally obtained product is 80-90%, and the purity of the finally obtained product is>95.0％。
(3) The diamine monomer is used as a raw material, and is polymerized with dianhydride at normal temperature to obtain polyamic acid, and then the polyamic acid is subjected to thermal imidization to obtain a polyimide film containing a pyridazine structure; the preparation process is simple, the yield is high, and the purity is high; the film not only keeps the excellent thermal property and mechanical property of the original polyimide, but also obviously improves the solubility and the light transmittance, and has wide application prospect.
Drawings
FIG. 1 Infrared spectrum of 4, 4' -bis (6-nitro-3-pyridazinoxy) diphenylmethane in example 1.
FIG. 2 Infrared spectrum of 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane in example 1.
FIG. 3 DSC of 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane in example 1.
FIG. 4 is a UV-Vis spectrum of high performance heterocyclic polyimide films 1 to 5 in examples 10 to 14.
Detailed Description
The present invention will be described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (11.99g) of 4,4 '-dihydroxydiphenylmethane, 130.56mmol (20.83g) of 3-chloro-2-nitropyridazine and 130.56mmol (18.04g) of potassium carbonate are dissolved in 1935mmol (180ml) of N, N' -dimethylacetamide, the total mass fraction of the solid in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 15g of crude dinitro product; dissolving the dinitro crude product and 6g of activated carbon in 861mmol (80ml) of N, N '-dimethylacetamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 4, 4' -bis (6-nitro-3-pyridazinoxy) diphenylmethane containing a pyridazine structure;
(2) under the protection of nitrogen, 15g of dinitro intermediate product containing a pyridazine structure is added into dioxane, 7.5g of palladium/carbon catalyst is added, 890mmol (45g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the hot filtration is carried out, the filtrate is cooled, solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours, 12g of 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane is obtained, the yield is 80%, and the purity is more than 99.0%.
The structural formula of the diamine monomer 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane containing pyridazine structure is as follows:
FIGS. 1 and 2 show the IR spectrum of 4,4 '-bis (6-nitro-3-pyridazinoxy) diphenylmethane (FIG. 1) and the IR spectrum of 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane (FIG. 2), respectively, comparing FIG. 1 with FIG. 2 at 3200-3500 cm-1The stretching vibration of the nitrogen-hydrogen bond between the two parts is 1600-1640 cm-1The bending contraction vibration of the nitrogen-hydrogen bond between the two compounds shows the existence of the amido, and proves that the nitro intermediate product is successfully reduced into the amido product; fig. 3 gives a DSC diagram for 4, 4' -bis (6-amino-3-pyridazinoxy) diphenylmethane with Tg 170 ℃.
Example 2
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (11.99g) of 3,3 '-dihydroxydiphenylmethane, 146.88mmol (23.43g) of 3-chloro-2-nitropyridazine and 146.88mmol (20.71g) of potassium carbonate are dissolved in 1613mmol (150ml) of N, N' -dimethylacetamide, the total mass fraction of the solid in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 12g of crude dinitro product; dissolving the dinitro crude product and 6g of activated carbon in 964mmol (90ml) of N, N '-dimethylacetamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 3, 3' -bis (6-nitro-3-pyridazinoxy) diphenylmethane containing a pyridazine structure;
(2) under the protection of nitrogen, 12g of dinitro intermediate product containing a pyridazine structure is added into dioxane, 7.2g of palladium/carbon catalyst is added, 959mmol (48g) of hydrazine hydrate is slowly dripped at the temperature of 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the thermal filtration is carried out, the filtrate is cooled, solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at the temperature of 50-100 ℃ for 5-10 hours, 10g of 3, 3' -bis (6-amino-3-pyridazinoxy) diphenylmethane is obtained, the yield is 83%, and the purity is more than 99.0%.
The structural formula of diamine monomer 3, 3' -di (6-amino-3-pyridazinoxy) diphenylmethane containing pyridazine structure is as follows:
example 3
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (15.14g) of 3-hydroxy-6- (4-hydroxyphenoxy) biphenyl, 163.20mmol (26.03g) of 3-chloro-2-nitropyridazine and 163.20mmol (23.01g) of potassium carbonate are dissolved in 1720mmol (160ml) of N, N' -dimethylacetamide, the total mass fraction of solids in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 14g of crude dinitro product; dissolving the dinitro crude product and 8.4g of activated carbon in 1286mmol (120ml) of N, N' -dimethylacetamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, filtering, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 3- (6-nitro-3-pyridazinoxy) -6- [4- (6-nitro-3-pyridazinoxy) phenoxy ] biphenyl containing a pyridazine structure;
(2) under the protection of N nitrogen, 14g of dinitro intermediate product containing a pyridazine structure is added into dioxane, 11.2g of palladium/carbon catalyst is added, 799mmol (40g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the hot filtration is carried out, the filtrate is cooled to separate out solid, the solid is filtered, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours to obtain 12g of 3- (6-amino-3-pyridazinoxy) -6- [4- (6-amino-3-pyridazinoxy) phenoxy ] biphenyl, the yield is 86%, and the purity is more than 99.0%.
The structural formula of diamine monomer 3- (6-amino-3-pyridazinoxy) -6- [4- (6-amino-3-pyridazinoxy) phenoxy ] biphenyl containing a pyridazine structure is as follows:
example 4
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (5.99g) of hydroquinone, 130.56mmol (20.83g) of 3-chloro-2-nitropyridazine and 130.56mmol (18.04g) of potassium carbonate are dissolved in 1935mmol (180ml) of N, N' -dimethylacetamide, the total mass fraction of solids in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 6g of crude dinitro product; dissolving the dinitro crude product and 2.4g of activated carbon in 344mmol (32ml) of N, N' -dimethylacetamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, filtering, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 1, 4-bis (6-nitro-3-pyridazinoxy) benzene containing a pyridazine structure;
(2) under the protection of nitrogen, 6g of dinitro intermediate product containing a pyridazine structure is added into dioxane, 3g of palladium/carbon catalyst is added, 599mmol (30g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the heat filtration is carried out, the filtrate is cooled, solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours, 5g of 1, 4-bis (6-amino-3-pyridazinoxy) benzene is obtained, the yield is 83%, and the purity is more than 99.0%.
The structural formula of diamine monomer 1, 4-di (6-amino-3-pyridazinoxy) benzene containing pyridazine structure is as follows:
example 5
(1) Under the protection of nitrogen at room temperature, 54.40mmol (5.99g) of resorcinol, 146.88mmol (23.43g) of 3-chloro-2-nitropyridazine and 146.88mmol (15.57g) of sodium carbonate are dissolved in 1720mmol (133ml) of N, N' -dimethylformamide, the total mass fraction of solids in the system is 10% -50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 7g of a crude dinitro product; dissolving the dinitro crude product and 3.5g of activated carbon in 562mmol (43ml) of N, N' -dimethylformamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 1, 3-bis (6-nitro-3-pyridazinoxy) benzene containing a pyridazine structure;
(2) under the protection of nitrogen, 7g of dinitro intermediate product containing a pyridazine structure is added into tetrahydrofuran, 5.6g of palladium/carbon catalyst is added, 699mmol (35g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the heat filtration is carried out, the filtrate is cooled, solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours, 6g of 1, 3-bis (6-amino-3-pyridazinoxy) benzene is obtained, the yield is 86%, and the purity is more than 99.0%.
The structural formula of diamine monomer 1, 3-di (6-amino-3-pyridazinoxy) benzene containing pyridazine structure is as follows:
example 6
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (16.01g) of 1, 4-bis (3-hydroxyphenoxy) benzene, 163.20mmol (26.03g) of 3-chloro-2-nitropyridazine and 163.20mmol (17.30g) of sodium carbonate are dissolved in 1613mmol (124ml) of N, N' -dimethylformamide, the total mass fraction of solids in the system is 10% -50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 16g of a crude dinitro product; dissolving the dinitro crude product and 9.6g of activated carbon in 1469mmol (113ml) of N, N' -dimethylformamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 1, 4-bis [3- (6-amino-3-pyridazinoxy) ] benzene containing a pyridazine structure;
(2) under the protection of nitrogen, 16g of dinitro intermediate product containing a pyridazine structure is added into tetrahydrofuran, 10g of palladium/carbon catalyst is added, 959mmol (48g) of hydrazine hydrate is slowly dripped at the temperature of 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the heat filtration is carried out, the filtrate is cooled, a solid is separated out, the filtration is carried out, a filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at the temperature of 50-100 ℃ for 5-10 hours, 13g of 1, 4-bis [3- (6-amino-3-pyridazinoxy) ] benzene is obtained, the yield is 81%, and the purity is more than 99.0%.
The structural formula of diamine monomer 1, 4-bis [3- (6-amino-3-pyridazinoxy) ] benzene containing pyridazine structure is as follows:
example 7
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (16.01g) of 1- (3-hydroxyphenoxy) -4- (4 '-hydroxyphenoxy) benzene, 130.56mmol (20.83g) of 3-chloro-2-nitropyridazine and 130.56mmol (13.84g) of sodium carbonate are dissolved in 1935mmol (149ml) of N, N' -dimethylformamide, the total mass fraction of solids in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 15g of crude dinitro product; dissolving the dinitro crude product and 6g of activated carbon in 861mmol (66ml) of N, N '-dimethylformamide, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 1- [3- (6-nitro-3-pyridazinoxy) phenoxy ] -4- [ 4' - (6-nitro-3-pyridazinoxy) phenoxy ] benzene containing a pyridazine structure;
(2) under the protection of nitrogen, 15g of dinitro intermediate product containing a pyridazine structure is added into tetrahydrofuran, 7.5g of palladium/carbon catalyst is added, 1199mmol (60g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the heat filtration is carried out, the filtrate is cooled, solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours, 12g of 1- [3- (6-amino-3-pyridazinoxy) phenoxy ] -4- [ 4' - (6-amino-3-pyridazinoxy) phenoxy ] benzene is obtained, the yield is 80%, and the purity is more than 99.0%.
The structural formula of diamine monomer 1- [3- (6-amino-3-pyridazinoxy) phenoxy ] -4- [ 4' - (6-amino-3-pyridazinoxy) phenoxy ] benzene containing pyridazine structure is as follows:
example 8
(1) Under the conditions of room temperature and nitrogen protection, 54.40mmol (10.13g) of biphenol, 146.88mmol (23.43g) of 3-chloro-2-nitropyridazine and 146.88mmol (8.24g) of potassium hydroxide are dissolved in 1720mmol (167ml) of N-methylpyrrolidone amine, the total mass fraction of solids in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 12g of crude dinitro product; dissolving the dinitro crude product and 6g of activated carbon in 964mmol (93ml) of N-methylpyrrolidone, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 4, 4' -bis (6-nitro-3-pyridazinoxy) biphenyl containing a pyridazine structure;
(2) under the protection of nitrogen, 12g of dinitro intermediate product containing a pyridazine structure is added into ethanol, 7.2g of palladium/carbon catalyst is added, 719mmol (36g) of hydrazine hydrate is slowly dripped at the temperature of 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the heat filtration is carried out, the filtrate is cooled, a solid is separated out, the filtration is carried out, a filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at the temperature of 50-100 ℃ for 5-10 hours, 10g of 4, 4' -bis (6-amino-3-pyridazinoxy) biphenyl is obtained, the yield is 83%, and the purity is more than 99.0%.
The structural formula of diamine monomer 4, 4' -bis (6-amino-3-pyridazinoxy) biphenyl containing a pyridazine structure is as follows:
example 9
(1) Under the protection of nitrogen at room temperature, 54.40mmol (18.29g) of hexafluorobisphenol A, 163.20mmol (26.03g) of 3-chloro-2-nitropyridazine and 163.20mmol (9.16g) of potassium hydroxide are dissolved in 1613mmol (156ml) of N-methylpyrrolidone, the total mass fraction of solids in the system is 10-50%, and then the mixture is heated to 60 ℃ to react for 6 hours; cooling to room temperature, pouring the reactant into a sodium hydroxide solution with the mass fraction of 5%, filtering, repeatedly washing the obtained solid with deionized water until the washing liquid is neutral, and obtaining 20g of crude dinitro product; dissolving the dinitro crude product and 8g of activated carbon in 1148mmol (111ml) of N-methylpyrrolidone, heating to 70-90 ℃, carrying out hot filtration after 30 minutes, dropwise adding water into the filtrate until the solution is saturated, carrying out filtration, and carrying out vacuum treatment on the obtained solid at 80 ℃ for 8 hours to obtain 2, 2' -bis [ (6-nitro-3-pyridazinoxy) benzene ] hexafluoropropane containing a pyridazine structure;
(2) under the protection of nitrogen, 20g of dinitro intermediate product containing a pyridazine structure is added into ethanol, 10g of palladium/carbon catalyst is added, 1199mmol (60g) of hydrazine hydrate is slowly dripped at 80 ℃ at the speed of 20-30 mL/h, the dripping is finished within 1.5-2 hours, the reaction is continued for 2-3 hours, then the hot filtration is carried out, the filtrate is cooled, a solid is separated out, the filtration is carried out, the filter cake is washed for 2-3 times by distilled water and is subjected to vacuum treatment at 50-100 ℃ for 5-10 hours, 16g of 2, 2' -bis [ (6-amino-3-pyridazinoxy) benzene ] hexafluoropropane is obtained, the yield is 80%, and the purity is more than 99.0%.
The structural formula of the diamine monomer 2, 2' -bis [ (6-amino-3-pyridazinoxy) benzene ] hexafluoropropane containing pyridazine structure is as follows:
example 10
(1) Dissolving 2mmol (0.7728g) of 4,4 ' -bis (6-amino-3-pyridazinoxy) diphenylmethane in 107mmol (10mL) of N, N ' -dimethylacetamide under a nitrogen atmosphere at room temperature, slowly adding 2mmol (0.8885) of 4,4 ' - (hexafluoroisopropylene) diphthalic anhydride after complete dissolution, and stirring for 12 hours to obtain a polyamic acid solution;
(2) pouring the polyamic acid solution onto a clean glass plate, leveling the polyamic acid solution with a scraper, and putting the glass plate into a program oven to remove a solvent and imidize the polyamic acid solution; the temperature-raising program is as follows: 5 hours at 60 ℃; at 80 ℃ for 2 hours; 2 hours at 100 ℃; 1 hour at 12 ℃; 200 ℃, 1 hour, 250 ℃, 1 hour; at 280 ℃ for 1 hour; and cooling to room temperature after imidization is finished, putting the glass plate into deionized water for demoulding to obtain an imidized film, and drying at 60 ℃ for 12 hours to obtain the high-performance heterocyclic polyimide film 1.
The structural formula of the high-performance heterocyclic polyimide film 1 is as follows:
Example 11
Example 10 was repeated using 2mmol (0.7728g) of 3,3 ' -bis (5-amino-2-pyridazinoxy) diphenylmethane in place of 4,4 ' -bis (6-amino-3-pyridazinoxy) diphenylmethane dissolved in 161mmol (15mL) of N, N ' -dimethylacetamide to give a high performance heterocyclic polyimide film 2.
The structural formula of the high-performance heterocyclic polyimide film 2 is as follows:
Example 12
Example 10 was repeated using 2mmol (0.9290g) of 3- (6-amino-3-pyridazinyloxy) -6- [4- (6-amino-3-pyridazinyloxy) phenoxy ] biphenyl in place of 4, 4' -bis (6-amino-3-pyridazinyloxy) diphenylmethane to give high performance heterocyclic polyimide film 3.
The structural formula of the high-performance heterocyclic polyimide film 3 is as follows:
Example 13
Example 10 was repeated using 2mmol (0.9609g) of 1- [3- (6-amino-3-pyridazinyloxy) phenoxy ] -4- [4 '- (6-amino-3-pyridazinyloxy) phenoxy ] benzene in place of 4, 4' -bis (6-amino-3-pyridazinyloxy) diphenylmethane to give high performance heterocyclic polyimide film 4.
The structural formula of the high-performance heterocyclic polyimide film 4 is as follows:
Example 14
Example 10 was repeated using 2mmol (0.9609g) of 1, 4-bis [3- (6-amino-3-pyridazinyloxy) ] benzene in place of 4, 4' -bis (6-amino-3-pyridazinyloxy) diphenylmethane to give high performance heterocyclic polyimide film 5.
The structural formula of the high-performance heterocyclic polyimide film 5 is as follows:
FIG. 4 shows the visible-UV spectra of the high performance heterocyclic polyimides prepared in examples 10-14. When the thickness of the film is 20 mu m, the transmittance of the film at 450nm is 77-83%, and the cutoff wavelength is 254-305 nm, so that high light transmittance is shown. The specific data are shown in Table 1.
TABLE 1 optical transmittances of high Performance polyimide films 1-5
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It should be understood by those skilled in the art that various changes and substitutions may be made in accordance with the technical solution and the inventive concept of the present invention, and the same properties or uses should be considered as the protection scope of the present invention.
Claims (2)
1. The application of the diamine monomer containing the pyridazine structure is characterized in that the diamine monomer containing the pyridazine structure is polymerized with dianhydride to obtain heterocyclic polyimide, and the structural formula of the heterocyclic polyimide is as follows:
the diamine monomer containing the pyridazine structure is one of 3- (6-amino-3-pyridazinoxy) -6- [4- (6-amino-3-pyridazinoxy) phenoxy ] biphenyl, 4 '-bis (6-amino-3-pyridazinoxy) diphenylmethane, 1- [3- (6-amino-3-pyridazinoxy) phenoxy ] -4- [ 4' - (6-amino-3-pyridazinoxy) phenoxy ] benzene and 1, 4-bis [3- (6-amino-3-pyridazinoxy) phenoxy ] benzene; the dianhydride is 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride.
2. The use of the diamine monomer containing a pyridazine structure of claim 1, wherein the heterocyclic polyimide film is prepared by the following steps:
(1) under the conditions of room temperature and nitrogen protection, dissolving a diamine monomer containing a pyridazine structure in a polar solvent, after completely dissolving, slowly adding dianhydride, and stirring for 12 hours to obtain a polyamic acid solution;
(2) pouring the polyamic acid solution onto a clean glass plate, leveling the polyamic acid solution with a scraper, and putting the glass plate into a program oven to remove a solvent and imidize the polyamic acid solution; the temperature-raising program is as follows: 5 hours at 60 ℃; at 80 ℃ for 2 hours; 2 hours at 100 ℃; at 120 ℃ for 1 hour; 200 ℃, 1 hour, 250 ℃, 1 hour; at 280 ℃ for 1 hour; cooling to room temperature after imidization is finished, putting the glass plate into deionized water for demoulding to obtain an imidized film, and drying at 60 ℃ for 12 hours to obtain a heterocyclic polyimide film;
the molar ratio of diamine monomer containing pyridazine structure, dianhydride and polar solvent is 1:1: 10-12; the polar solvent is one of N, N '-dimethylacetamide, N' -dimethylformamide and N-methylpyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328488.4A CN107056711B (en) | 2017-05-11 | 2017-05-11 | Diamine monomer containing pyridazine group and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328488.4A CN107056711B (en) | 2017-05-11 | 2017-05-11 | Diamine monomer containing pyridazine group and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107056711A CN107056711A (en) | 2017-08-18 |
| CN107056711B true CN107056711B (en) | 2020-07-07 |
Family
ID=59597645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710328488.4A Active CN107056711B (en) | 2017-05-11 | 2017-05-11 | Diamine monomer containing pyridazine group and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107056711B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861415A (en) * | 2021-09-26 | 2021-12-31 | 上海极紫科技有限公司 | Polyamide acid resin capable of imidizing at low temperature for negative photoresist and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053470B (en) * | 2018-08-06 | 2020-03-31 | 吉林大学 | Flexible diamine monomer, preparation method thereof and application thereof in preparation of polyimide |
| CN109608648A (en) * | 2018-12-06 | 2019-04-12 | 太原理工大学 | A kind of polyimide material and preparation method thereof with temperature response performance |
| CN111834531B (en) * | 2019-04-15 | 2022-04-19 | 天津大学 | Organic semiconductor material, preparation method and application |
| CN112500568B (en) * | 2020-12-24 | 2021-08-17 | 中国科学院长春应用化学研究所 | Polyimide film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102488A (en) * | 2013-02-07 | 2013-05-15 | 江西师范大学 | High dielectric constant polyimide containing bipyrimidine structure and preparation method |
| CN103113309A (en) * | 2013-02-07 | 2013-05-22 | 江西师范大学 | Bipyrimidyl dibenzene/diether/diamine and synthesis method thereof |
| CN105061302A (en) * | 2015-08-27 | 2015-11-18 | 哈尔滨工程大学 | Pyridine-ring-containing diamine, polyimide prepared from pyridine-ring-containing diamine and preparation method of polyimide |
| CN105301906A (en) * | 2015-11-10 | 2016-02-03 | 杭州福斯特光伏材料股份有限公司 | Positive type photosensitive polyimide resin composition |
| CN106589372A (en) * | 2016-11-29 | 2017-04-26 | 江西师范大学 | Polyimide containing two pyrimidine rings and preparation method thereof |
-
2017
- 2017-05-11 CN CN201710328488.4A patent/CN107056711B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102488A (en) * | 2013-02-07 | 2013-05-15 | 江西师范大学 | High dielectric constant polyimide containing bipyrimidine structure and preparation method |
| CN103113309A (en) * | 2013-02-07 | 2013-05-22 | 江西师范大学 | Bipyrimidyl dibenzene/diether/diamine and synthesis method thereof |
| CN105061302A (en) * | 2015-08-27 | 2015-11-18 | 哈尔滨工程大学 | Pyridine-ring-containing diamine, polyimide prepared from pyridine-ring-containing diamine and preparation method of polyimide |
| CN105301906A (en) * | 2015-11-10 | 2016-02-03 | 杭州福斯特光伏材料股份有限公司 | Positive type photosensitive polyimide resin composition |
| CN106589372A (en) * | 2016-11-29 | 2017-04-26 | 江西师范大学 | Polyimide containing two pyrimidine rings and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| High transparent polyimides containing pyridine and biphenyl units: Synthesis, thermal, mechanical, crystal and optical properties;Yue Guan等;《Polymer》;20150216;第61卷;1-10 * |
| Highly transparent polyimides derived from 2-phenyl-4,6-bis(4-aminophenoxy)pyrimidine and 1,3-bis(5-amino-2-pyridinoxy)benzene: preparation, characterization, and optical properties;Chunbo Wang等;《RSC Advances》;20151118;第5卷(第125期);103246-103254 * |
| Novel soluble polyimides containing pyridine and fluorinated units: preparation, characterization, and optical and dielectric properties;Weibing Dong等;《RSC Advances》;20160217;第6卷(第26期);21662-21671 * |
| Novel soluble polyimides derived from 2,2 "-bis[4-(5-amino-2-pyridinoxy)phenyl]hexafluoropropane: Preparation, characterization, and optical, dielectric properties;Yue Guan等;《Polymer》;20140703;第55卷(第16期);3634-3641 * |
| Synthesis and characterization of novel polyimides derived from 3,6-bis(4-aminophenoxy)pyridazine;Yue Guan等;《High Performance Polymers》;20140601;第26卷(第4期);455-462 * |
| 主链含吡啶杂环结构聚酰亚胺的合成及性能研究;管月;《吉林大学博士学位论文》;20150815;21-96 * |
| 含哒嗪环聚酰亚胺的合成及性能表征;管月等;《高分子学报》;20140630(第6期);838-843 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861415A (en) * | 2021-09-26 | 2021-12-31 | 上海极紫科技有限公司 | Polyamide acid resin capable of imidizing at low temperature for negative photoresist and preparation method thereof |
| CN113861415B (en) * | 2021-09-26 | 2023-05-19 | 上海极紫科技有限公司 | Polyamic acid resin capable of being aminated by low Wen Ya and used for negative photoresist and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107056711A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107056711B (en) | Diamine monomer containing pyridazine group and preparation method and application thereof | |
| Tullos et al. | Thermal conversion of hydroxy-containing imides to benzoxazoles: polymer and model compound study | |
| JP6086139B2 (en) | Polyimide precursor and polyimide | |
| CN103193674B (en) | Many cyano group diamine monomer and preparation and application thereof | |
| TW201231505A (en) | Liquid crystal alignment agent, liquid crystal alignment film and a liquid crystal display element, and compounds and polymers used in manufacture of those | |
| JP5845918B2 (en) | Polyimide precursor and polyimide | |
| CN105085281A (en) | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation | |
| Wang et al. | Synthesis and properties of new fluorene-based polyimides containing trifluoromethyl and isopropyl substituents | |
| WO2002051909A1 (en) | Diamines, polyimide precursors and polyimides produced by using the diamines, and liquid crystal aligning agents | |
| CN113387977B (en) | Diamine and preparation method thereof, and polyimide and preparation method thereof | |
| Wu et al. | Synthesis and characterization of novel star-branched polyimides derived from 2, 2-bis [4-(2, 4-diaminophenoxy) phenyl] hexafluoropropane | |
| CN118388411A (en) | Amide-containing nitrogen heterocyclic diamine compound, and preparation method and application thereof | |
| CN105130885A (en) | Aromatic diamine containing bipyridyl structure and synthesis method thereof | |
| WO2002051908A1 (en) | Diaminobenzene derivatives, polyimide precursors and polyimides prepared by using tha same, and liquid crystal aligning agents | |
| CN112409315B (en) | Diamine monomer containing spirofluorene functional group, preparation method thereof and polyimide with low dielectric constant | |
| CN111961061A (en) | Novel dianhydride compound and preparation method and application thereof | |
| CN112679734A (en) | Soluble polyimide containing bis (trifluoromethyl) benzene substituted asymmetric meta-position structure and preparation method thereof | |
| CN116730845A (en) | High-fluorine-content biphenyl diamine, colorless polyimide optical film, and preparation method and application thereof | |
| CN115677514B (en) | Fluorine-containing diamine monomer, polyimide film and preparation method | |
| WO2007034716A1 (en) | Soluble transparent polybenzoxazole precursor, polybenzoxazole and methods for producing those | |
| TW202248191A (en) | Meta-ester aromatic diamines, method for producing same, and polyimide having said meta-ester aromatic diamines as raw material | |
| CN108976135B (en) | Flexible diamine monomer, preparation method thereof and application thereof in preparation of polyimide | |
| CN101560166B (en) | Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene | |
| CN101580474B (en) | Preparation method of 1,4-bis(2-trifluoromethyl-4-aminophenoxyl)benzene | |
| CN112898198B (en) | Nitrogen-containing aromatic heterocyclic nitro compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |