CN112225897A - Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof - Google Patents
Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof Download PDFInfo
- Publication number
- CN112225897A CN112225897A CN202011120665.8A CN202011120665A CN112225897A CN 112225897 A CN112225897 A CN 112225897A CN 202011120665 A CN202011120665 A CN 202011120665A CN 112225897 A CN112225897 A CN 112225897A
- Authority
- CN
- China
- Prior art keywords
- compound
- trifluoromethyl
- aromatic diamine
- substituted aromatic
- diamine compound
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The application provides a trifluoromethyl substituted aromatic diamine compound containing an aromatic ester structure and a preparation method thereof, relating to the field of organic synthesis. The trifluoromethyl substituted aromatic diamine compound has both an aromatic ester structure and trifluoromethyl, and has a stable structure. The structural characteristics of the polyaramid or polyimide prepared by the trifluoromethyl substituted aromatic diamine compound are that the main chain contains a polar aryl ester structure and a high heat-resistant trifluoromethyl large side group is hung on the main chain, so that the prepared polyaramid or polyimide has better solubility in a polar aprotic solvent while keeping high heat resistance. Namely, the aromatic polyamide and polyimide prepared by the aromatic diamine compound have good dissolving and film-forming properties, excellent thermal stability and mechanical properties, and are expected to be applied to new-generation microelectronic packaging materials and flexible display materials.
Description
Technical Field
The application relates to the field of organic synthesis, in particular to a trifluoromethyl substituted aromatic diamine compound containing an aromatic ester structure and a preparation method thereof.
Background
The polyaramid and the polyimide are both heat-resistant high polymer materials with excellent comprehensive performance. Since the six and seventies of the last century began to be industrialized, they have been applied in various fields, in particular, as high-performance fibers, high heat-resistant composite material substrates and electronic packaging materials, which have been widely applied in the industries of aerospace, machinery, microelectronics, petrochemical industry and the like. Although such high temperature resistant materials have excellent comprehensive properties, most of polyaramids and polyimides have high melting temperature and are insoluble in organic solvents due to the rigid main chain structure, strong intermolecular interaction and close packing of molecular chains, so that the molding processing of the polyaramids and the polyimides is difficult. This limits their further use in the relevant fields, in particular in high temperature resistant films. In order to overcome these disadvantages and to prepare polyaramids and polyimides with good processability and excellent comprehensive properties, researchers have invested great efforts.
Generally, in order to improve the solubility of polyaramid and polyimide materials, on one hand, a flexible structure is introduced to a polyaramid and polyimide main chain, the segmental rotation energy is reduced, segmental motion is facilitated, the regularity of a molecular chain can be damaged to a certain extent, and the solubility performance is improved. On the other hand, large side groups are introduced into the main chains of the polyaramid and the polyimide, which is the most common method for improving the solubility of the polyaramid and the polyimide, and the large side groups effectively destroy the regularity of molecular chains, so that the molecular chains are stacked more loosely, which is beneficial to the infiltration of solvents, thereby enhancing the solubility of materials. Although polyaramid and polyimide can show good solubility by introducing a flexible structure and large side groups into a molecular chain, the heat resistance of the material is reduced to a certain extent, and the application range of the material is influenced.
Disclosure of Invention
The present application aims to provide a trifluoromethyl substituted aromatic diamine compound containing an aromatic ester structure and a preparation method thereof, so as to solve the technical problems.
In order to achieve the above object, the present application provides a trifluoromethyl substituted aromatic diamine compound containing an aromatic ester structure, which has a general structural formula as follows:
wherein R is1、R2、R3、R4、R5、R6、R7And R8Are independently selected from H or CF3And R is1、R2、R3、R4、R5、R6、R7And R8At least one of them being CF3。
In some embodiments of the present application, the trifluoromethyl-substituted aromatic diamine compound comprises:
in some embodiments of the present application, a method for preparing the trifluoromethyl-substituted aromatic diamine compound comprises: reacting a compound A with a compound B to obtain a compound C, and carrying out hydrogenation reaction on the compound C to obtain the trifluoromethyl substituted aromatic diamine compound;
the structural general formula of the compound A is as follows:
the structural general formula of the compound B is as follows:
the structural general formula of the compound C is as follows:
in some embodiments of the present application, the reaction system of the compound a and the compound B further comprises a dehydrating agent, a first catalyst, and a first solvent;
preferably, the dehydrating agent is dicyclohexylcarbodiimide;
preferably, the first catalyst is 4-dimethylaminopyridine;
preferably, the first solvent is dichloromethane;
preferably, the temperature condition of the reaction of the compound A and the compound B is 20-80 ℃, and the reaction time is 3-8 h.
In some embodiments of the present application, the hydrogenation reaction comprises:
mixing materials including the compound C, a second solvent and a second catalyst, and introducing hydrogen to react to obtain the trifluoromethyl substituted aromatic diamine compound;
preferably, the temperature of the hydrogenation reaction is 30-80 ℃, and the reaction time is 4-8 h;
preferably, the second solvent comprises tetrahydrofuran;
preferably, the second catalyst comprises Pd/C;
preferably, the amount of the second catalyst is 1-10% of the mass of the compound C;
preferably, the pressure of the hydrogen is 0.1-0.7 MPa.
In some embodiments of the present application, the method of preparing compound a comprises: reacting a compound D with a first nitrate to obtain a compound A; the structural general formula of the compound D is as follows:
the preparation method of the compound B comprises the following steps: reacting the compound E with a second nitrate to obtain a compound B; the structural general formula of the compound E is as follows:
preferably, the first nitrate and the second nitrate are both Cu (NO)3)2·3H2O。
In some embodiments of the present application, the compound D has the structural formula:
the preparation method of the compound D comprises the following steps: mixing raw materials including benzoic acid, trifluoroacetic acid, sodium thiosulfate and titanium dioxide, and then reacting under ultraviolet irradiation to obtain a compound D;
the structural formula of the compound E is as follows:
the preparation method of the compound E comprises the following steps: mixing raw materials including phenol, a third solvent, sodium trifluoromethanesulfonate and dichlorodicyanobenzoquinone, and then reacting under the irradiation of visible light to obtain a compound E;
preferably, the third solvent is acetonitrile.
Optionally, the wavelength of the ultraviolet light is 190-400 nm.
Optionally, the wavelength of the visible light is 780-400 nm.
The application also provides polyimide obtained by polymerizing raw materials including the trifluoromethyl substituted aromatic diamine compound.
The present application also provides a polyaramid obtained by polymerizing raw materials including the trifluoromethyl substituted aromatic diamine compound.
The present application also provides an epoxy resin curing agent comprising the trifluoromethyl substituted aromatic diamine compound.
The epoxy resin obtained by curing the epoxy resin curing agent has higher heat resistance.
The beneficial effect of this application:
the trifluoromethyl substituted aromatic diamine compound containing the aromatic ester structure provided by the application has the aromatic ester structure and the trifluoromethyl, and is stable in structure. The structural characteristics of the polyaramid or polyimide prepared by the trifluoromethyl substituted aromatic diamine compound are that the main chain contains a polar aryl ester structure and a high heat-resistant trifluoromethyl large side group is hung on the main chain, so that the prepared polyaramid or polyimide has better solubility in a polar aprotic solvent while keeping high heat resistance. Namely, the aromatic polyamide and polyimide prepared by the aromatic diamine compound have good dissolving and film-forming properties, excellent thermal stability and mechanical properties, and are expected to be applied to new-generation microelectronic packaging materials and flexible display materials.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 shows a scheme for preparing phenyl 4,4 '-diamino-3' -trifluoromethylbenzoate obtained in example 1 of the present application1H NMR spectrum.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by weight" means the basic unit of measure indicating the relationship of the mass ratio of the plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the parts by weight of the component A are a parts and the parts by weight of the component B are B parts, the ratio of the mass of the component A to the mass of the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is not to be understood that, unlike the parts by weight, the sum of the parts by weight of all components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The term "plurality" refers to two or more.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 14 Synthesis of phenyl 4,4 '-diamino-3' -trifluoromethylbenzoate
(1) Phenol (37.6g) was dissolved in acetonitrile (1000ml) and sodium trifluoromethylsulfinate (CF) was added3SO2Na) (31.2g), dichlorodicyanobenzoquinone (22.7g), 800mW/cm-2Reaction was carried out at 25 ℃ for 24 hours under irradiation with visible light to give 3-trifluoromethylphenol (8.42g) in 13% yield.
(2) 3-Trifluoromethylphenol (4.2g) was dissolved in tetrahydrofuran, and Cu (NO) was added3)2·3H2O (20.42g) was reacted at 25 ℃ for 6 hours to give 3-trifluoromethyl-4-nitrophenol (3.65g) in 68% yield.
(3) 4-Nitrobenzoic acid (4.00g) and 3-trifluoromethyl-4-nitrophenol (4.96g) were added to 90ml of methylene chloride, Dicyclohexylcarbodiimide (DCC) (4.94g) and 4-Dimethylaminopyridine (DMAP) (0.03g) were added to react at 30 ℃ for 6 hours, and phenyl 4,4 '-dinitro-3' -trifluoromethylbenzoate (8.53g) was obtained by filtration, concentration and recrystallization, with a yield of 85%.
(4) Phenyl 4,4 '-dinitro-3' -trifluoromethylbenzoate (10.00g) was added to 100ml of tetrahydrofuran, 10% Pd/C (0.80g) was added thereto, and hydrogen gas of 0.7MPa was introduced at 70 ℃ to react for 3 hours, followed by filtration and concentration to obtain phenyl 4,4 '-diamino-3' -trifluoromethylbenzoate (7.82g) in 94% yield. Preparation of phenyl 4,4 '-diamino-3' -trifluoromethylbenzoate prepared in this example1The H NMR spectrum is shown in FIG. 1.
The synthetic route is as follows:
example Synthesis of phenyl 24, 4 '-diamino-3, 3' -bis (trifluoromethyl) benzoate
(1) Benzoic acid (18.3g),Trifluoroacetic acid (600ml), sodium thiosulfate (7.14g), titanium dioxide (TiO)2) (4.8g) the mixture is added into a flask and reacts for 24 hours at room temperature under the radiation of 365nm ultraviolet light, and 3-trifluoromethyl-benzoic acid (5.43g) is obtained by column chromatography separation with the yield of 18 percent.
(2) 3-trifluoromethyl-benzoic acid (5.2g) was dissolved in tetrahydrofuran and Cu (NO) was added3)2·3H2O (21.55g) was reacted at 25 ℃ for 6 hours to give 3-trifluoromethyl-4-nitrobenzoic acid (3.86g) in 60% yield.
(3) Phenol (37.6g) was dissolved in acetonitrile (1000ml) and sodium trifluoromethylsulfinate (CF) was added3SO2Na) (31.2g), dichlorodicyanobenzoquinone (22.7g), 800mW/cm-2Reaction was carried out at 25 ℃ for 24 hours under irradiation with visible light to give 3-trifluoromethylphenol (7.78g) in 12% yield.
(4) 3-Trifluoromethylphenol (4.2g) was dissolved in tetrahydrofuran, and Cu (NO) was added3)2·3H2O (20.42g) was reacted at 25 ℃ for 6 hours to give 3-trifluoromethyl-4-nitrophenol (3.65g) in 68% yield.
(5) 3-trifluoromethyl-4-nitrobenzoic acid (4.20g) and 3-trifluoromethyl-4-nitrophenol (3.70g) were added to 80ml of dichloromethane, Dicyclohexylcarbodiimide (DCC) (3.68g) and 4-Dimethylaminopyridine (DMAP) (0.04g) were added and reacted at 40 ℃ for 5 hours, filtered, concentrated and recrystallized to give 4,4 '-dinitro-3, 3' -bis (trifluoromethyl) benzoate (6.37g) in 84% yield.
(6) 4,4 '-dinitro-3, 3' -bis (trifluoromethyl) benzoate (10.00g) was added to 100ml of tetrahydrofuran, 5% Pd/C (1.50g) was added thereto, and 0.5MPa of hydrogen was introduced at 70 ℃ to react for 6 hours, followed by filtration and concentration to obtain 4,4 '-diamino-3, 3' -bis (trifluoromethyl) benzoate (8.33g) in 97% yield.
The synthetic route is as follows:
example Synthesis of phenyl 34, 4' -diamino-2, 3',6' -tris (trifluoromethyl) benzoate
(1) Benzoic acid (18.3g), trifluoroacetic acid (6)00ml), sodium thiosulfate (7.14g), titanium dioxide (TiO)2) (4.8g) the mixture is added into a flask and reacts for 24 hours at room temperature under the radiation of 313nm ultraviolet light, and 3-trifluoromethyl-benzoic acid (4.56g) is obtained by column chromatography separation with the yield of 16 percent.
(2) 3-trifluoromethyl-benzoic acid (5.2g) was dissolved in tetrahydrofuran and Cu (NO) was added3)2·3H2O, at 25 ℃ for 6h to give 3-trifluoromethyl-4-nitrobenzoic acid (3.86g) in 60% yield.
(3) Phenol (37.6g) was dissolved in acetonitrile (1000ml) and sodium trifluoromethylsulfinate (CF) was added3SO2Na) (62.4g), dichlorodicyanobenzoquinone (22.7g), 800mW/cm-2Reaction was carried out at 25 ℃ for 24 hours under irradiation with visible light to give 3, 5-bis (trifluoromethyl) phenol (7.78g) in 12% yield.
(4) 3, 5-bis (trifluoromethyl) phenol (4.2g) was dissolved in tetrahydrofuran, and Cu (NO) was added3)2·3H2O (20.42g) was reacted at 25 ℃ for 6h to give 3, 5-bis (trifluoromethyl) -4-nitrophenol (3.65g) in 68% yield.
(5) 2-trifluoromethyl-4-nitrobenzoic acid (4.00g) and 3, 5-bis (trifluoromethyl) -4-nitrophenol (4.68g) were added to 87ml of dichloromethane, Dicyclohexylcarbodiimide (DCC) (4.96g) and 4-Dimethylaminopyridine (DMAP) (0.15g) were added, reacted at 60 ℃ for 6h, filtered, concentrated and recrystallized to give phenyl 4,4' -dinitro-2, 3',5' -tris (trifluoromethyl) benzoate (6.70g) in 80% yield.
(6) 4,4 '-dinitro-2, 3',6 '-tris (trifluoromethyl) benzoate (10.00g) was added to 100ml of tetrahydrofuran, 10% Pd/C (1.00g) was added thereto, and 0.6MPa of hydrogen was introduced at 60 ℃ to react for 4 hours, followed by filtration and concentration to obtain 4,4' -diamino-2, 3',6' -tris (trifluoromethyl) benzoate (8.34g) in 95% yield.
The synthetic route is as follows:
example 4 Synthesis of polyimide PI-1
4,4 '-diamino-3' -trifluoromethylphenyl benzoate (15mmol) and 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (15mmol) prepared in example 1 were added to a 500-ml three-necked round-bottomed flask, respectively, which was dried and charged with nitrogen, and N-methylpyrrolidone (50ml) was added as a solvent to react at room temperature for 4 hours to obtain a polyamic acid solution, acetic anhydride (15mmol) was added as a dehydrating agent and pyridine (30mmol) was added as a catalyst to react at 120 ℃ for 4 hours to obtain a polyimide solution, the polyimide solution was poured into water, the precipitate was collected by suction filtration, washed with boiling water for several times, and vacuum-dried to obtain a powdery polyimide PI-1.
EXAMPLE 5 Synthesis of polyimide PI-2
Respectively adding 4,4 '-diamino-3, 3' -bis (trifluoromethyl) benzoate (15mmol) and 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (15mmol) prepared in example 2 into a 500-ml three-neck round-bottom flask which is dried and is filled with nitrogen, adding N-methylpyrrolidone (50ml) as a solvent, reacting for 4h at room temperature to obtain a polyamic acid solution, adding acetic anhydride (15mmol) as a dehydrating agent and pyridine (30mmol) as a catalyst, reacting for 4h at 120 ℃ to obtain a polyimide solution, pouring the polyimide solution into water, collecting precipitates through suction filtration, soaking and washing for many times by boiling water, and drying in vacuum to obtain powdery polyimide PI-2.
EXAMPLE 6 Synthesis of polyimide PI-3
Respectively adding 4,4' -diamino-2, 3',6' -tris (trifluoromethyl) benzoate (15mmol) and 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (15mmol) prepared in example 3 into a 500-ml three-neck round-bottom flask which is dried and is filled with nitrogen, adding N-methylpyrrolidone (50ml) as a solvent, reacting for 4 hours at room temperature to obtain a polyamic acid solution, adding acetic anhydride (15mmol) as a dehydrating agent and pyridine (30mmol) as a catalyst, reacting for 4 hours at 120 ℃ to obtain a polyimide solution, pouring the polyimide solution into water, collecting precipitates through suction filtration, soaking and washing for multiple times by using boiling water, and drying in vacuum to obtain powdery polyimide PI-3.
Comparative example 1 Synthesis of polyimide PI-4
Respectively adding 4,4' -diaminodiphenylmethane (15mmol) and 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (15mmol) into a 500ml three-neck round-bottom flask which is dried and is filled with nitrogen, adding N-methylpyrrolidone (50ml) as a solvent, reacting for 4h at room temperature to obtain a polyamic acid solution, adding acetic anhydride (15mmol) as a dehydrating agent and pyridine (30mmol) as a catalyst, reacting for 4h at 120 ℃ to obtain a polyimide solution, pouring the polymer solution into water, collecting precipitates by suction filtration, soaking and washing for many times by using boiling water, and drying in vacuum to obtain powdery polyimide PI-4.
Evaluation of polyimide Properties
(1) Solubility evaluation method:
weighing a plurality of parts of equivalent polyimide resin powder, respectively placing the parts in different solvents to prepare polyimide resin solutions with 5% solid content, and observing the dissolution conditions of the polyimide resin in the different solvents by adopting mechanical stirring for 2 hours at 25 ℃.
(2) Mechanical property evaluation method:
the mechanical properties of the polyimide were tested using an electronic universal material tester (Instron 5567): tensile rate 5mm/min, load 100N, gauge length 20mm, and approximately 20 μm thick film was cut into 60mm by 10mm wide strip samples.
(3) Method for evaluating Heat resistance:
the thermal stability of the polyimide was tested using a thermogravimetric analyzer (Du Pont TGA 2100): the measurement temperature range is 100-800 ℃, and the heating rate is 20 ℃/min under the nitrogen flow. Temperature T at 5% mass loss5The polyimide material was evaluated for heat resistance.
TABLE 1 dissolution of polyimide resins prepared in examples 4 to 6 and comparative example 1 in different solvents
NMP: n-methyl pyrrolidone; DMAc: n, N-dimethylacetamide; DMF: n, N-dimethylformamide; DMSO, DMSO: dimethyl sulfoxide; THF: tetrahydrofuran.
As can be seen from Table 1, the polyimide resins prepared in examples 4 to 6 of the present application have good solubility in solvents such as N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and the like.
TABLE 2 Heat resistance and mechanical Properties of polyimide resins prepared in examples 4 to 6 and comparative example 1
| Resin type | T5(℃) | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 4(PI-1) | 545 | 126 | 23 |
| Example 5(PI-2) | 552 | 128 | 26 |
| Example 6(PI-3) | 558 | 131 | 26 |
| COMPARATIVE EXAMPLE 1(PI-4) | 520 | 119 | 21 |
As can be seen from Table 2, the polyimide resins prepared in examples 4-6 of the present application all have better thermal stability and mechanical properties.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A trifluoromethyl substituted aromatic diamine compound containing an aromatic ester structure is characterized in that the structural general formula is as follows:
wherein R is1、R2、R3、R4、R5、R6、R7And R8Are independently selected from H or CF3And R is1、R2、R3、R4、R5、R6、R7And R8At least one of them being CF3。
2. The trifluoromethyl substituted aromatic diamine compound of claim 1 wherein the trifluoromethyl substituted aromatic diamine compound comprises:
3. the method for producing a trifluoromethyl-substituted aromatic diamine compound according to any one of claims 1 to 2, which comprises: reacting a compound A with a compound B to obtain a compound C, and carrying out hydrogenation reaction on the compound C to obtain the trifluoromethyl substituted aromatic diamine compound;
the structural general formula of the compound A is as follows:
the structural general formula of the compound B is as follows:
the structural general formula of the compound C is as follows:
4. the method for producing a trifluoromethyl-substituted aromatic diamine compound according to claim 3, wherein the reaction system of the compound A and the compound B further contains a dehydrating agent, a first catalyst and a first solvent;
preferably, the dehydrating agent is dicyclohexylcarbodiimide;
preferably, the first catalyst is 4-dimethylaminopyridine;
preferably, the first solvent is dichloromethane;
preferably, the temperature condition of the reaction of the compound A and the compound B is 20-80 ℃, and the reaction time is 3-8 h.
5. The method of producing a trifluoromethyl-substituted aromatic diamine compound according to claim 3, wherein the hydrogenation reaction comprises:
mixing materials including the compound C, a second solvent and a second catalyst, and introducing hydrogen to react to obtain the trifluoromethyl substituted aromatic diamine compound;
preferably, the temperature of the hydrogenation reaction is 30-80 ℃, and the reaction time is 4-8 h;
preferably, the second solvent comprises tetrahydrofuran;
preferably, the second catalyst comprises Pd/C;
preferably, the amount of the second catalyst is 1-10% of the mass of the compound C;
preferably, the pressure of the hydrogen is 0.1-0.7 MPa.
6. The method for producing a trifluoromethyl-substituted aromatic diamine compound according to claim 3, wherein the method for producing the compound a comprises: reacting a compound D with a first nitrate to obtain a compound A; the structural general formula of the compound D is as follows:
the preparation method of the compound B comprises the following steps: reacting the compound E with a second nitrate to obtain a compound B; the structural general formula of the compound E is as follows:
preferably, the first nitrate and the second nitrate are both Cu (NO)3)2·3H2O。
7. The method for producing a trifluoromethyl-substituted aromatic diamine compound according to claim 6, wherein the compound D has the formula:
the preparation method of the compound D comprises the following steps: mixing raw materials including benzoic acid, trifluoroacetic acid, sodium thiosulfate and titanium dioxide, and then reacting under ultraviolet irradiation to obtain a compound D;
the structural formula of the compound E is as follows:
the preparation method of the compound E comprises the following steps: mixing raw materials including phenol, a third solvent, sodium trifluoromethanesulfonate and dichlorodicyanobenzoquinone, and then reacting under the irradiation of visible light to obtain a compound E;
preferably, the third solvent is acetonitrile.
8. A polyimide obtained by polymerizing a raw material including the trifluoromethyl-substituted aromatic diamine compound according to any one of claims 1 to 2.
9. A polyaramid obtained by polymerizing a raw material including the trifluoromethyl-substituted aromatic diamine compound according to any one of claims 1 to 2.
10. An epoxy resin curing agent comprising the trifluoromethyl substituted aromatic diamine compound according to any one of claims 1 to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011120665.8A CN112225897A (en) | 2020-10-19 | 2020-10-19 | Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011120665.8A CN112225897A (en) | 2020-10-19 | 2020-10-19 | Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112225897A true CN112225897A (en) | 2021-01-15 |
Family
ID=74118650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011120665.8A Pending CN112225897A (en) | 2020-10-19 | 2020-10-19 | Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225897A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232017A (en) * | 2021-03-15 | 2022-10-25 | 华为技术有限公司 | Compound, resin, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185471A (en) * | 1991-03-15 | 1993-02-09 | Occidental Chemical Corporation | Method for ether formation |
| JP2008101187A (en) * | 2006-09-19 | 2008-05-01 | Asahi Kasei Corp | Polyesterimide and method for producing the same |
| CN108026273A (en) * | 2015-09-24 | 2018-05-11 | 旭化成株式会社 | The manufacture method of polyimide precursor, resin combination and resin film |
| CN110003470A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院长春应用化学研究所 | A kind of polyimide material and preparation method thereof applied to flexible display substrates |
| CN110198926A (en) * | 2017-01-27 | 2019-09-03 | 胜高科技股份有限公司 | Diamine compound and the polyimide compound and molding for using it |
-
2020
- 2020-10-19 CN CN202011120665.8A patent/CN112225897A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185471A (en) * | 1991-03-15 | 1993-02-09 | Occidental Chemical Corporation | Method for ether formation |
| JP2008101187A (en) * | 2006-09-19 | 2008-05-01 | Asahi Kasei Corp | Polyesterimide and method for producing the same |
| CN108026273A (en) * | 2015-09-24 | 2018-05-11 | 旭化成株式会社 | The manufacture method of polyimide precursor, resin combination and resin film |
| CN110198926A (en) * | 2017-01-27 | 2019-09-03 | 胜高科技股份有限公司 | Diamine compound and the polyimide compound and molding for using it |
| CN110003470A (en) * | 2019-04-29 | 2019-07-12 | 中国科学院长春应用化学研究所 | A kind of polyimide material and preparation method thereof applied to flexible display substrates |
Non-Patent Citations (1)
| Title |
|---|
| 彭治汉 施祖培: "《塑料工业手册 聚酰胺》", 31 December 2001, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232017A (en) * | 2021-03-15 | 2022-10-25 | 华为技术有限公司 | Compound, resin, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6037499A (en) | Aromatic diamines and polyimides based on 4,4'-bis-(4-aminophenoxy)-2,2' or 2,2',6,6'-substituted biphenyl | |
| Liaw et al. | Synthesis and characterization of new polyamide-imides containing pendent adamantyl groups | |
| Banerjee et al. | Synthesis and properties of fluorinated polyimides. 3. Derived from novel 1, 3-bis [3′-trifluoromethyl-4′(4 ″-amino benzoxy) benzyl] benzene and 4, 4-bis [3′-trifluoromethyl-4′(4-amino benzoxy) benzyl] biphenyl | |
| Saxena et al. | Synthesis and characterization of polyamides and poly (amide–imide) s derived from 2, 2-bis (4-aminophenoxy) benzonitrile | |
| Hsiao et al. | Synthesis and properties of novel poly (amide-imide) s containing pendent diphenylamino groups | |
| Zhou et al. | Synthesis and characterization of transparent polyimides derived from ester-containing dianhydrides with different electron affinities | |
| Wen et al. | Syntheses and characterizations of cardo polyimides based on new spirobifluorene diamine monomer | |
| US5145916A (en) | Terminal-modified imide oligomer composition | |
| CN112225897A (en) | Trifluoromethyl substituted aromatic diamine compound containing aromatic ester structure and preparation method thereof | |
| Liaw et al. | Synthesis and characterization of new soluble cardo poly (amide–imide) s derived from 2, 2-bis [4-(4-trimellitimidophenoxy) phenyl] norbornane | |
| Dezern | Synthesis and characterization of BTDA‐based polyamide‐imides | |
| US5710334A (en) | Aromatic dinitro and diamino intermediates | |
| Chen et al. | Synthesis, characterization and properties of polyimides with spirobisbenzoxazole scaffold structure | |
| Li et al. | Organo-soluble and transparent polyimides containing phenylphosphine oxide and trifluoromethyl moiety: Synthesis and characterization | |
| Varma et al. | Phosphorus-containing imide resins. I | |
| JP2011102259A (en) | Aromatic diamine compound and manufacturing method for the same, and synthetic resin | |
| Liaw et al. | Novel Organosoluble Poly (amide‐imide) s Derived from Kink Diamine Bis [4‐(4‐trimellitimidophenoxy) phenyl]‐diphenylmethane. Synthesis and Characterization | |
| Guo et al. | New fluorinated xanthene-containing polybenzoxazoles with low dielectric constants | |
| Hsiao et al. | A novel class of organosoluble and light-colored fluorinated polyamides derived from 2, 2′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl or 2, 2′-bis (4-amino-2-trifluoromethylphenoxy)-1, 1′-binaphthyl | |
| US5844065A (en) | 2,2'-dimethyl-4,4'-bis (4-aminophenoxy) biphenyl, and polymers prepared therefrom by polycondensation | |
| Kausar et al. | Facile synthesis and properties of a new generation of soluble and thermally stable polyimides | |
| Tan et al. | Synthesis, characterization, and properties of novel aromatic polyamides containing phthalazinone moiety | |
| Wang et al. | Synthesis and properties of soluble poly [bis (benzimidazobenzisoquinolinones)] based on novel aromatic tetraamine monomers | |
| JPS6375034A (en) | Addition-curing soluble imide oligomer and intermediate material for fiber-reinforced composite material using said oligomer | |
| Mutar | A Study of Synthesis and Characterization of New Aromatic Poly (amide-imide) s |
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 |