CN112225676B - Fluorine-containing aromatic diamine compound and preparation method thereof, fluorine-containing polyimide compound and preparation method thereof - Google Patents

Fluorine-containing aromatic diamine compound and preparation method thereof, fluorine-containing polyimide compound and preparation method thereof Download PDF

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CN112225676B
CN112225676B CN202011120650.1A CN202011120650A CN112225676B CN 112225676 B CN112225676 B CN 112225676B CN 202011120650 A CN202011120650 A CN 202011120650A CN 112225676 B CN112225676 B CN 112225676B
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aromatic diamine
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CN112225676A (en
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王胜林
黎厚明
王建新
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Shenzhen Dalton Electronic Materials Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
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    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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    • 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
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    • 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
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    • 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

Abstract

The invention provides a fluorine-containing aromatic diamine compound and a preparation method thereof, and a fluorine-containing polyimide compound and a preparation method thereof. The fluorine-containing aromatic diamine compound has a structural general formula as follows:
Figure DDA0002731905410000011
the preparation method comprises the following steps: mixing materials including the compound A and the compound B, carrying out a first reaction to obtain a compound C, and then carrying out a hydrogenation reaction on the compound C. The fluorine-containing polyimide compound comprises a fluorine-containing aromatic diamine compound as a raw material. The preparation method comprises the following steps: mixing materials including the fluorine-containing aromatic diamine compound and the dianhydride compound to obtain a mixture, and then carrying out a sixth reaction to obtain a prepolymer; and (3) performing dehydration cyclization reaction on the prepolymer, and performing post-treatment to obtain the fluorine-containing polyimide compound. The polyimide compound prepared from the fluorine-containing aromatic diamine compound has good solubility and higher permeabilityExcessive rate and good mechanical property.

Description

Fluorine-containing aromatic diamine compound and preparation method thereof, fluorine-containing polyimide compound and preparation method thereof
Technical Field
The invention relates to the field of organic synthesis, and in particular relates to a fluorine-containing aromatic diamine compound and a preparation method thereof, and a fluorine-containing polyimide compound and a preparation method thereof.
Background
Amine compounds are important raw materials for synthesizing a plurality of nitrogen-containing compounds, play an important role in organic and pharmaceutical synthesis, and are widely applied to synthesis of biochemical products and natural products. Amines and their derivatives are widely used in the synthesis of high molecular materials, pesticides, pharmaceuticals, dyes, food additives, and the like.
Polyimide is widely used as a high polymer material with high heat resistance, good chemical stability, excellent mechanical properties and electrical properties in the aspects of insulating materials and structural materials. Has been widely applied to the high and new technical fields of aviation, aerospace, electric, microelectronics and the like. Although the polyimide has various varieties and various synthesis routes, the polyimide structure can be divided into dianhydride (or tetracarboxylic acid) and diamine monomers. Therefore, the polyimide has excellent structure designability, and functional groups can be introduced through the structure design of comonomer molecules, so that the performance of the polyimide material in certain aspect can be enhanced.
Among them, it is one of the important points of research to obtain polyimide materials with good solubility by the structural design of comonomer molecules.
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide a fluorine-containing aromatic diamine compound and a preparation method thereof, and a fluorine-containing polyimide compound and a preparation method thereof, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a fluorine-containing aromatic diamine compound has a structural general formula as follows:
Figure GDA0003912914130000021
wherein R is 1 -R 8 Each independently selected from hydrogen or trifluoromethyl, and R 1 -R 8 At least one of which is trifluoromethyl.
Alternatively, R 1 -R 8 Can be both trifluoromethyl or R 1 -R 8 Of which 1,2, 3, 4, 5,6, 7 or 8 are trifluoromethyl.
The preparation method of the fluorine-containing aromatic diamine compound comprises the following steps:
mixing materials including a compound A and a compound B, carrying out a first reaction to obtain a compound C, and then carrying out a hydrogenation reaction on the compound C to obtain the fluorine-containing aromatic diamine compound;
the structural general formula of the compound A is as follows:
Figure GDA0003912914130000022
the structural general formula of the compound B is as follows:
Figure GDA0003912914130000031
the structural general formula of the compound C is as follows:
Figure GDA0003912914130000032
wherein R is 1 -R 8 Each independently selected from hydrogen or trifluoromethyl, and R 1 -R 8 At least one of which is trifluoromethyl.
Preferably, the preparation method of the compound A comprises the following steps:
mixing materials including the compound D, a first solvent, magnesium powder, iodine and methyl iodide, heating for a second reaction, cooling, and introducing carbon dioxide gas for a third reaction to obtain a compound E;
carrying out a fourth reaction on the compound E and thionyl chloride to obtain a compound A;
the structural general formula of the compound D is as follows:
Figure GDA0003912914130000033
the structural general formula of the compound E is as follows:
Figure GDA0003912914130000041
in the compound A, B, C, D, E, each substituent corresponds to a substituent in the general structural formula of the fluorine-containing aromatic diamine compound.
Preferably, the first solvent comprises anhydrous tetrahydrofuran;
preferably, the second reaction is carried out under an inert atmosphere;
preferably, the inert atmosphere comprises nitrogen and/or argon;
preferably, the temperature of the second reaction is 30-60 ℃, and the reaction time is 2-4h;
preferably, the third reaction is carried out under ice salt bath conditions, and the reaction time is 1.5-2.5h;
preferably, after the third reaction is finished, the method further comprises: filtering and concentrating the reaction system, and then washing the solid with a second solvent to obtain the compound E;
preferably, the second solvent comprises petroleum ether;
preferably, the fourth reaction is carried out under reflux for a reaction time of 1.5 to 2.5h.
Alternatively, the temperature of the second reaction may be any value between 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 30-60 ℃, and the reaction time may be any value between 2h, 3h, 4h and 2-4h; the reaction time of the third reaction can be any value between 1.5h, 2.0h, 2.5h and 1.5-2.5h; the reaction time of the fourth reaction may be any value between 1.5h, 2.0h, 2.5h and 1.5-2.5h.
Preferably, the preparation method of the compound B comprises the following steps:
mixing materials including a compound F, cuprous chloride or cuprous iodide, potassium fluoride or potassium carbonate, liquid ammonia and a third solvent, and heating to perform a fifth reaction to obtain a compound B;
the structural general formula of the compound F is as follows:
Figure GDA0003912914130000051
each substituent in the compound F corresponds to a substituent in the general structural formula of the fluorine-containing aromatic diamine compound.
Preferably, the temperature of the fifth reaction is 100-200 ℃, and the reaction time is 4-6h;
preferably, the third solvent comprises an aqueous ethanol solution;
preferably, the volume ratio of ethanol to water in the ethanol aqueous solution is (4-6): 1;
preferably, the processing after the fifth reaction further includes: concentrating the reaction system, extracting by using a fourth solvent, washing with water, and concentrating to obtain a compound B;
preferably, the fourth solvent comprises ethyl acetate.
Alternatively, the temperature of the fifth reaction may be any value between 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and 100-200 ℃, and the reaction time may be any value between 4h, 5h, 6h and 4-6h; the volume ratio of ethanol to water in the ethanol aqueous solution may be 4: 1. 5: 1. 6:1 and (4-6): 1, or any value between.
Preferably, the time of the first reaction is 2-6h;
preferably, the material of the first reaction further comprises a fifth solvent and an alkaline substance;
preferably, the fifth solvent comprises anhydrous toluene and/or dichloromethane;
preferably, the alkaline substance comprises sodium bicarbonate and/or sodium carbonate;
preferably, the first reaction also comprises water washing and concentration treatment after the first reaction is finished;
preferably, the hydrogenation reaction comprises: mixing materials including the compound C, a sixth solvent and a catalyst, and introducing hydrogen to react to obtain the fluorine-containing aromatic diamine compound;
preferably, the temperature of the hydrogenation reaction is 40-100 ℃, and the reaction time is 4-8h;
preferably, the sixth solvent comprises tetrahydrofuran;
preferably, the catalyst comprises a palladium on carbon catalyst;
preferably, the amount of the palladium-carbon catalyst is 5 to 10 percent of the mass of the compound C;
preferably, the pressure of the hydrogen is from 0.5 to 1MPa.
Alternatively, the time of the first reaction may be any value between 2h, 3h, 4h, 5h, 6h and 2-6h; the temperature of the hydrogenation reaction can be any value between 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and 40-100 ℃, and the reaction time can be any value between 4h, 5h, 6h, 7h, 8h and 4-8h; the amount of the palladium-carbon catalyst can be any one of 5%, 6%, 7%, 8%, 9%, 10% and 5% -10% of the mass of the compound C; the pressure of the hydrogen gas may be any of 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, and 0.5-1MPa.
A fluorine-containing polyimide compound, the raw material of which comprises the fluorine-containing aromatic diamine compound;
preferably, the fluorine-containing polyimide compound has a general structural formula:
Figure GDA0003912914130000061
wherein R is 1 -R 8 Each aloneSelected from hydrogen or trifluoromethyl, and R 1 -R 8 At least one of them is trifluoromethyl; a represents a dianhydride residue; n is 50 to 500;
more preferably, the fluorine-containing polyimide compound has the structural formula:
Figure GDA0003912914130000071
wherein n =50-500.
A method for preparing the fluorine-containing polyimide compound comprises the following steps:
mixing materials including the fluorine-containing aromatic diamine compound and the dianhydride compound to obtain a mixture, and then carrying out a sixth reaction to obtain a prepolymer;
and (3) performing dehydration cyclization reaction on the prepolymer, and performing post-treatment to obtain the fluorine-containing polyimide compound.
Preferably, a seventh solvent is also included in the mixture;
preferably, the seventh solvent comprises N-methylpyrrolidone;
preferably, the solids content of the mixture is 5-20wt%;
preferably, the time of the sixth reaction is 1-6h;
preferably, the dianhydride-based compound comprises an aromatic dianhydride-based compound, and the structural general formula of the aromatic dianhydride-based compound is as follows:
Figure GDA0003912914130000072
a is aromatic dianhydride residue;
preferably, the dehydrating agent used in the dehydrative cyclization reaction comprises acetic anhydride;
preferably, the catalyst used for the dehydrative ring-closure reaction comprises pyridine;
preferably, the temperature of the dehydration cyclization reaction is 80-110 ℃, and the reaction time is 2-5h;
preferably, the post-processing comprises:
precipitating the product of the dehydrocyclization reaction in an eighth solvent, filtering to obtain a solid, soaking and washing by using a ninth solvent, and drying to obtain a powdery fluorine-containing polyimide compound;
preferably, the eighth solvent comprises water;
preferably, the ninth solvent comprises ethanol;
preferably, the drying is carried out by adopting a vacuum oven under reduced pressure, the drying temperature is 55-65 ℃, and the drying time is 10-14h.
Alternatively, the solids content of the mixture may be any value between 5wt%, 10wt%, 15wt%, 20wt% and 5-20wt%; the time of the sixth reaction can be any value between 1h, 2h, 3h, 4h, 5h, 6h and 1-6h; the temperature of the dehydration cyclization reaction can be any value between 80 ℃, 90 ℃, 100 ℃, 110 ℃ and 80-110 ℃, and the reaction time can be any value between 2h, 3h, 4h, 5h and 2-5h; the drying temperature can be any value between 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃ and 55-65 ℃, and the drying time can be any value between 10h, 11h, 12h, 13h, 14h and 10-14h.
Compared with the prior art, the invention has the beneficial effects that:
the fluorine-containing aromatic diamine compound provided by the application has an aromatic amide structure and a trifluoromethyl substituent, and because a fluorine atom has a smaller atomic radius, a smaller electron polarizability and high electronegativity, the fluorine-containing aromatic diamine compound is prepared by introducing the trifluoromethyl substituent (-CF) 3 ) The introduction of bulky side groups or side chains can prevent polyimide molecular chains from being tightly arranged, and effectively reduce the interaction force among the molecular chains, thereby improving the solubility and the transparency of the polyimide molecular chains;
the preparation method of the fluorine-containing aromatic diamine compound provided by the application is simple in process;
the fluorine-containing polyimide compound provided by the application has good transparency, good solubility, higher transmittance and good mechanical properties;
the preparation method of the fluorine-containing polyimide compound provided by the application is simple in process;
the fluorine-containing aromatic diamine compound is used for preparing fluorine-containing polyimide compounds, and various polyimide compounds can be obtained.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is the 4,4 '-diamino-2' -trifluoromethylbenzanilide obtained in example 2 1 An H NMR spectrum;
FIG. 2 is the 4,4 '-diamino-2,2' -bistrifluoromethylbenzanilide obtained in example 3 1 HNMR atlas.
Detailed Description
The term 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 of the claims rather than immediately after the subject matter, it defines only the elements described in that 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise specified, 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 mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g, 2.689g, and the like. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is 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 unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the 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).
Embodiments of the present invention 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 invention and should not be construed as limiting the scope of the present invention. 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 1
Bromination reaction
50g of 1-bromine-2,3,5,6-tetramethyl-4-nitrobenzene is added into a three-neck flask with a cooling reflux device, the temperature is raised to 200 ℃, 387g of bromine is dropwise added, and the temperature is reduced to the room temperature after the dropwise addition is finished. Adding 300g of petroleum ether into the reaction system for extraction to obtain an extract, adding 100g of sodium hypobromite and 500g of water, stirring for reaction for 50h, concentrating in vacuum, and passing through a column by using ethyl acetate petroleum ether as an eluent to obtain 60g of yellow 1-bromo-2,3,5,6-tetratribromomethyl-4-nitrobenzene.
The reaction formula is shown as follows:
Figure GDA0003912914130000111
trifluoromethyl substitution reaction
60g of the product from step I are added to 100ml of N-methylpyrrolidone and heated to 100 ℃. 160g of antimony trifluoride is added in batches, the reaction process is violent in heat release, and the reaction is stirred for 2 hours. After the reaction, the reaction mixture was cooled to room temperature and concentrated by vacuum distillation to obtain 13.1g of a yellow product, 1-bromo-2,3,5,6-tetra-trifluoromethyl-4-nitrobenzene.
The reaction formula is shown as follows:
Figure GDA0003912914130000112
III. Synthesis of Carboxylic acids
And (3) adding 10g of the product obtained in the step (II) into 100ml of anhydrous tetrahydrofuran, adding 3g of magnesium powder, 0.1g of iodine and 0.1g of methyl iodide, heating to 50 ℃ under the protection of nitrogen to initiate reaction, and keeping the temperature for 3 hours. Then cooling, introducing carbon dioxide gas under the condition of ice salt bath, reacting for 2h, filtering, concentrating, and washing with petroleum ether to obtain white solid 1-carboxyl-2,3,5,6-tetra-trifluoromethyl-4-nitrobenzene 9.5g.
The reaction formula is shown as follows:
Figure GDA0003912914130000121
IV. Synthesis of Amines
And (3) adding 10g of the product obtained in the step (II) into a mixed system of 100ml of ethanol and 20ml of water, adding 10g of cuprous chloride, 20g of potassium fluoride and 45g of liquid ammonia, and heating to 180 ℃ for reaction for 5 hours. Concentrating, extracting with ethyl acetate, washing with water, and concentrating to obtain 8g of 1-amino-2,3,5,6-tetra-trifluoromethyl-4-nitrobenzene.
The reaction formula is shown as follows:
Figure GDA0003912914130000122
v. synthesis of acyl chloride and amide
And (3) adding 50ml of thionyl chloride into 10g of the product obtained in the step III, heating and refluxing for 2h, distilling out excessive thionyl chloride to obtain acyl chloride, adding 100ml of anhydrous toluene, adding 10g of the product obtained in the step IV, adding 5g of sodium bicarbonate, stirring for 4h, washing with water, and concentrating to obtain 18.2g of amidated product.
The reaction formula is shown as follows:
Figure GDA0003912914130000123
Figure GDA0003912914130000131
VI hydrogenation reaction
Adding 10g of amidation product into 100ml of tetrahydrofuran, adding 1g of palladium carbon as a catalyst, pressurizing to 0.6MPa, reacting at 60 ℃, filtering after 6h of hydrogenation, and concentrating the filtrate to obtain 4.6g of target product.
The reaction formula is shown as follows:
Figure GDA0003912914130000132
example 2
Trifluoromethyl substitution
50g 4-nitroaniline, 150g 1, 2-dichloroethane as solvent, and facial-tris (2-phenylpyridine) iridium complex (fac-Ir (ppy) 3 ) 3.8g asAdding 20g K as catalyst 2 CO 3 19.4g of trifluoroiodomethane were first mixed with 50g of 1, 2-dichloroethane and slowly added. And reacting for 24 hours at room temperature under the condition of blue illumination. After filtration, concentration was carried out to obtain 50.2g of 2-amino-5-nitrobenzotrifluoride.
The reaction formula is shown as follows:
Figure GDA0003912914130000133
synthesis of carboxylic acids
Adding 1-bromo-4-nitrobenzene into 15g to 100ml of anhydrous tetrahydrofuran, adding 4.5g of magnesium powder, 0.1g of iodine and 0.1g of methyl iodide, introducing nitrogen for protection, heating to 50 ℃ for initiating reaction, and preserving heat for 3 hours. Then cooling, introducing carbon dioxide gas under the condition of ice salt bath, reacting for 2h, filtering, concentrating and washing with petroleum ether to obtain 13.5g of 1-carboxyl-4-nitrobenzene white solid.
The reaction formula is shown as follows:
Figure GDA0003912914130000141
III Synthesis of acyl chlorides and amides
Adding 15g of 1-carboxyl-4-nitrobenzene into 50ml of thionyl chloride, heating and refluxing for 2h, distilling out the redundant thionyl chloride to obtain acyl chloride, adding 150ml of anhydrous toluene, then adding 18g of 2-amino-5-nitrobenzotrifluoride, then adding 5g of sodium bicarbonate, stirring for 4h, washing with water, and concentrating to obtain 25g of an amide product.
The reaction formula is shown as follows:
Figure GDA0003912914130000142
IV hydrogenation reaction
Adding 20g of the amide product obtained in the step III into 150ml of tetrahydrofuran, adding 1g of palladium carbon as a catalyst, pressurizing to 0.6MPa, reacting at 80 ℃, filtering after 6h of hydrogenation, and concentrating the filtrate to obtain 10.5g of 4,4 '-diamino-2' -trifluoromethylbenzanilide, wherein the nuclear magnetic resonance hydrogen spectrum of the product is shown in the attached figure 1.
The reaction formula is shown as follows:
Figure GDA0003912914130000151
example 3
Trifluoromethyl substitution
50g of 4-nitroaniline is added into a reaction device which is filled with inert gas and protected by argon, then 150g of 1, 2-dichloroethane is added as a solvent, and the facial-tris (2-phenylpyridine) iridium complex (fac-Ir (ppy) 3 ) 3.8g of the catalyst was added, and 20g K was added 2 CO 3 19.4g of trifluoroiodomethane were first mixed with 50g of 1, 2-dichloroethane and slowly added. The reaction was carried out under blue light conditions at room temperature for 24h. After filtration, concentration was carried out to obtain 50.2g of 2-amino-5-nitrobenzotrifluoride.
The reaction formula is shown as follows:
Figure GDA0003912914130000152
nitration reaction
Under the condition of normal temperature and in a stirring state, 30g of concentrated H 2 SO 4 (98 wt%) slowly dropping 16g of fuming nitric acid to prepare nitrated mixed acid, slowly dropping 50g of o-bromotrifluorotoluene into the mixed acid at 50 ℃, keeping the temperature for reaction for 5h, separating the liquid after the reaction is finished, washing an upper layer organic phase with 5% sodium carbonate aqueous solution, washing the upper layer organic phase with water to be neutral, and distilling to obtain 56.2g of yellow product 2-bromo-5-nitrotrifluorotoluene.
III. Synthesis of Carboxylic acids
Adding 2-bromo-5-nitrobenzotrifluoride into 20g to 100ml of anhydrous tetrahydrofuran, adding 5g of magnesium powder, 0.1g of iodine and 0.1g of methyl iodide, heating to 50 ℃ under the protection of nitrogen gas to initiate reaction, and preserving heat for 3 hours. Then cooling, introducing carbon dioxide gas under the condition of ice salt bath, reacting for 2h, filtering, concentrating and washing with petroleum ether to obtain 16.5g of 2-carboxyl-5-nitrobenzotrifluoride white solid.
IV. synthesis of acyl chlorides and amides
Adding 20g of 2-carboxyl-5-nitrotrifluorotoluene into 100ml of thionyl chloride, heating and refluxing for 2h, distilling out redundant thionyl chloride to obtain acyl chloride, adding 150ml of anhydrous toluene, then adding 18g of 2-amino-5-nitrotrifluorotoluene, then adding 5g of sodium bicarbonate, stirring for 4h, washing with water, and concentrating to obtain 24g of amide product.
The reaction formulae of the steps II to IV are shown below:
Figure GDA0003912914130000161
v. hydrogenation reaction
And (3) adding 20g of the product obtained in the step (IV) into 100ml of tetrahydrofuran, adding 1g of palladium carbon as a catalyst, pressurizing to 0.6MPa, reacting at 100 ℃, filtering after 10h of hydrogenation is finished, and concentrating the filtrate to obtain 10.8g of the target product 4,4 '-diamino-2,2' -bistrifluoromethyl benzanilide, wherein the nuclear magnetic resonance hydrogen spectrum of the target product is shown in the attached figure 2.
The reaction formula is shown as follows:
Figure GDA0003912914130000171
synthesis of polyimide PI-1:
the 4,4 '-diamino-2,2' -bistrifluoromethylbenzanilide obtained in example 3 was reacted with hexafluorodianhydride (6 FDA) to obtain polyimide PI-1, which was specifically prepared as follows:
in a reactor equipped with a nitrogen blanket, 18.2g (50 mmol) of 4,4 '-diamino-2,2' -bistrifluoromethylbenzanilide and 161.6g of NMP were charged, and stirred at room temperature for 30min to confirm complete dissolution. Then, 22.2g (50 mmol) of hexafluorodianhydride (6 FDA) was added thereto, and the reaction was stirred at room temperature for 4 hours to obtain a transparent viscous polyamic acid solution having a solid content of 20% by weight.
The structural formula of hexafluorodianhydride (6 FDA) is:
Figure GDA0003912914130000172
the obtained polyamic acid solution was further added with 28.28g of NMP (N-methylpyrrolidone), and then 15.32g (150 mmol) of acetic anhydride and 23.73g (300 mmol) of pyridine were added, and the reaction was carried out at room temperature for 2 hours to carry out chemical imidization, thereby obtaining a polyimide solution. And after the reaction is finished, pouring the reaction solution into a large amount of pure water for precipitation, filtering out polyimide solids after precipitation, soaking and washing twice by using a large amount of ethanol, filtering, and drying for 12 hours in a reduced-pressure vacuum oven at 60 ℃ to obtain powdery polyimide PI-1.
The structural formula of the polyimide PI-1 is as follows:
Figure GDA0003912914130000181
wherein n =50-500.
Comparative example 1
4,4' -diaminobenzanilide was used in place of 4,4' -diamino-2,2 ' -bis-trifluoromethylbenzanilide provided in example 3 of this application, and reacted with hexafluorodianhydride (6 FDA) to give polyimide PI-2, the structural formula of which is as follows:
Figure GDA0003912914130000182
comparative example 2
The polyimide PI-3 was obtained by reacting 4,4 '-diamino-2,2' -bistrifluoromethylbenzanilide provided in example 3 of this application with 4,4 '-diamino-2,2' bistrifluoromethylbiphenyl, having the following structural formula:
Figure GDA0003912914130000183
comparative examples 1 and 2 differ from example 4 in the use of a different diamine monomer, and the mass of the diamine monomer and NMP added was slightly varied to obtain the same reaction solids content. The differences and comparison of the amounts are shown in Table 1, and the other working conditions are identical. In comparative examples 1 and 2, powdery polyimides PI-2 and PI-3 were obtained, respectively.
Table 1 comparison of example 3 with comparative examples 1 and 2 at different dosages
Figure GDA0003912914130000191
The polyimide PI-1, PI-2 and PI-3 samples obtained in example 3, comparative example 1 and comparative example 2 were weighed to obtain equal amounts of polyimide powder, and the equal amounts of the polyimide powder were placed in different solvents respectively to prepare polyimide solutions with 5% solid content, and the dissolution of the polyimide powder in the different solvents was observed at 25 ℃ by mechanical stirring for 2 hours, as shown in Table 2:
TABLE 2 dissolution of polyimide resins in different solvents
Figure GDA0003912914130000192
The dried polyimide obtained in example 3 was dissolved in NMP to prepare a polyimide solution having a solid content of 20%. The polyimide solution was applied to a glass substrate by a spin coater to form a film. Then removing the solvent at high temperature to obtain the colorless transparent polyimide film. High temperature drying using a circulating oven, drying procedure: 80 ℃/1h, 150 ℃/30min, 200 ℃/30min and 250 ℃/30min. And taking out the polyimide film from the oven, naturally cooling the polyimide film to room temperature, and controlling the thickness of the dry film to be 15-20 mu m to obtain the polyimide film PI-1. The dried polyimides obtained in comparative examples 1 and 2 were used to prepare polyimide films PI-2 and PI-3 in the same manner as described above.
The polyimide films PI-1, PI-2 and PI-3 were tested for their performance, and the results are shown in Table 3 below:
table 3 polyimide film test data
Figure GDA0003912914130000201
TABLE 4 mechanical Property test results of polyimide films
Figure GDA0003912914130000202
As can be seen from the test results in tables 2,3, and 4, the polyimide obtained in example 3 of the present application has good solubility in the above solvents, high transmittance, and good mechanical properties, as compared to the polyimides obtained in comparative examples 1 and 2.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled 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 invention.
Furthermore, 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 invention 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 invention 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 (9)

1. A fluorine-containing polyimide polymer, characterized in that the structural formula of the fluorine-containing polyimide polymer is as follows:
Figure F_221116084846557_557537001
；
wherein n =50-500.
2. A method for producing a fluorine-containing polyimide polymer according to claim 1, comprising:
mixing materials including the fluorine-containing aromatic diamine compound and the dianhydride compound to obtain a mixture, and then carrying out a sixth reaction to obtain a prepolymer;
performing dehydration cyclization reaction on the prepolymer, and performing post-treatment to obtain the fluorine-containing polyimide polymer;
the structural formula of the fluorine-containing aromatic diamine compound is as follows:
Figure F_221116084846654_654228002
；
the structural formula of the dianhydride compound is as follows:
Figure F_221116084846779_779235003
。
3. the method according to claim 2, wherein the method for producing the fluorine-containing aromatic diamine compound comprises:
mixing materials including a compound A and a compound B, carrying out a first reaction to obtain a compound C, and then carrying out a hydrogenation reaction on the compound C to obtain the fluorine-containing aromatic diamine compound;
the structural formula of the compound A is as follows:
Figure F_221116084846875_875898004
；
the structural formula of the compound B is as follows:
Figure F_221116084847101_101002005
；
the structural formula of the compound C is as follows:
Figure F_221116084847327_327572006
。
4. the process according to claim 3, wherein the process for the preparation of compound a comprises:
mixing materials including the compound D, a first solvent, magnesium powder, iodine and methyl iodide, heating for a second reaction, cooling, and introducing carbon dioxide gas for a third reaction to obtain a compound E;
carrying out a fourth reaction on the compound E and thionyl chloride to obtain a compound A;
the structural formula of the compound D is as follows:
Figure F_221116084847404_404233007
；
the structural formula of the compound E is as follows:
Figure F_221116084847498_498497008
。
5. the method of claim 4, wherein the first solvent comprises anhydrous tetrahydrofuran;
the second reaction is carried out in an inert atmosphere; the inert atmosphere comprises nitrogen and/or argon; the temperature of the second reaction is 30-60 ℃, and the reaction time is 2-4h; the third reaction is carried out under the condition of ice salt bath, and the reaction time is 1.5-2.5h; after the third reaction is finished, the method further comprises the following steps: filtering and concentrating the reaction system, and then washing the solid with a second solvent to obtain the compound E; the second solvent comprises petroleum ether; the fourth reaction is carried out in a reflux state, and the reaction time is 1.5-2.5h.
6. The method according to any one of claims 3 to 5, wherein the first reaction time is 2 to 6 hours;
the material of the first reaction also comprises a fifth solvent and an alkaline substance;
the fifth solvent comprises anhydrous toluene and/or dichloromethane;
the alkaline substance comprises sodium bicarbonate and/or sodium carbonate;
and after the first reaction is finished, water washing and concentration treatment are also included.
7. The production method according to any one of claims 3 to 5, wherein the hydrogenation reaction comprises: mixing materials including the compound C, a sixth solvent and a catalyst, and introducing hydrogen to react to obtain the fluorine-containing aromatic diamine compound;
the temperature of the hydrogenation reaction is 40-100 ℃, and the reaction time is 4-8h;
the sixth solvent comprises tetrahydrofuran;
the catalyst comprises a palladium on carbon catalyst;
the dosage of the palladium carbon catalyst is 5 to 10 percent of the mass of the compound C;
the pressure of the hydrogen is 0.5-1MPa.
8. The method of claim 2, wherein the mixture further comprises a seventh solvent;
the seventh solvent comprises N-methylpyrrolidone;
the solids content of the mixture is 5-20wt%;
the time of the sixth reaction is 1-6h;
the dehydrating agent used in the dehydration cyclization reaction comprises acetic anhydride;
the catalyst used for the dehydration cyclization reaction comprises pyridine;
the temperature of the dehydration cyclization reaction is 80-110 ℃, and the reaction time is 2-5h.
9. The method of manufacturing according to claim 2, wherein the post-treatment comprises:
precipitating the product of the dehydration cyclization reaction in an eighth solvent, filtering to obtain a solid, soaking and washing by using a ninth solvent, and drying to obtain the powdery fluorine-containing polyimide polymer;
the eighth solvent comprises water;
the ninth solvent comprises ethanol;
the drying is carried out by adopting a vacuum oven under reduced pressure, the drying temperature is 55-65 ℃, and the drying time is 10-14h.
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Publication number Priority date Publication date Assignee Title
DE2416811A1 (en) * 1974-04-06 1975-10-30 Bayer Ag Trifluoromethyl gp-contg. filament-forming aromatic polyamides - opt. contg. heterocyclic gps. prepd. by polycondensation in polar organic solvents
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