CN114478278B - Carbonyl-containing polysubstituted aromatic diamine monomer and preparation method thereof - Google Patents
Carbonyl-containing polysubstituted aromatic diamine monomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbonyl-containing polysubstituted aromatic diamine monomer and a preparation method thereof, wherein the structural formula of the carbonyl-containing polysubstituted aromatic diamine monomer is shown in the specification
Wherein R is 1 、R 2 is-H, -CF 3 、‑OCH 3 Or one of the alkyl radicals, R 3 Is one of aryl or alkyl, ar 1 、Ar 2 Is an aromatic ring or an aromatic heterocyclic ring. The invention provides two preparation methods, one is a base catalysis synthesis method, and the other is an ionic liquid catalysis method. The diamine monomer can be applied to the preparation of a high-performance polyimide film material containing a carbonyl structure, and can further improve the potential application values of the prepared polyimide film material such as the dissolution film-forming property, the optical transparency, the tensile strength property, the dielectric loss property and the like.
Description
Technical Field
The invention relates to the field of diamine monomer preparation, in particular to a carbonyl-containing polysubstituted aromatic diamine monomer and a preparation method thereof.
Background
Polyimide is a polymer containing a polyimide ring on a main chain, is an organic high polymer material, can resist high temperature of more than 400 ℃, has high insulation performance within a long-term use temperature range of 200-300 ℃, is called as one of the most promising engineering plastics in the 21 st century, is widely used in the fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membranes, laser and the like at present, and becomes a necessary special engineering material.
The polyimide film is mainly prepared by reacting aromatic diamine with aromatic dianhydride, aromatic tetracarboxylic acid or aromatic tetracarboxylic dialkyl ester, a prepreg forming process is usually adopted in the preparation process, and the aprotic polar solvents with high boiling points are difficult to volatilize completely in the prepreg preparation process, and volatile matters are also released during the cyclization of polyamic acid, so that pores are easy to generate in a composite material product, and a high-quality composite material without pores is difficult to obtain.
Meanwhile, although polyimide has extremely excellent properties, it is too costly compared to other polymers, which results in great limitations in the development of polyimide.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a carbonyl-containing polysubstituted aromatic diamine monomer, which is a novel carbonyl-containing polysubstituted aromatic diamine monomer structure, and a carbonyl asymmetric diamine structure is introduced, so that different functional groups can be introduced into a molecular chain of a polymer by the carbonyl-containing polysubstituted aromatic diamine monomer, and the polyimide with the asymmetric structure prepared by the method has good solubility, flexibility, processability, higher tensile strength and lower dielectric loss.
The second purpose of the invention is to provide two preparation methods of the carbonyl-containing polysubstituted aromatic diamine monomer, the first method provided by the invention is to adopt strong base as a catalyst and then heat up for reaction to prepare a target monomer, the second method provided by the invention is a green synthesis method adopting a basic ionic liquid catalyst, the two preparation methods provided by the invention have low energy consumption and low cost, and the prepared monomer has high purity and is worthy of wide popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a carbonyl-containing polysubstituted aromatic diamine monomer, which has the structural formula:
wherein R is 1 、R 2 is-H, -CF 3 、-OCH 3 Or one of the alkyl radicals, R 3 Is one of aryl or alkyl, ar 1 、Ar 2 Is an aromatic ring or an aromatic heterocyclic ring.
Preferably, ar 1 、Ar 2 Is one of the following groups, wherein the substitution positions of the same aromatic ring are different:
preferably, when Ar 1 Is selected as
When, ar 2 Is selected as
One of them, the structural formula of the diamine monomer prepared by the method is as follows:
preferably, in order to obtain the polyimide film with excellent properties such as dielectric constant, dielectric loss and the like, the polyimide film is optimized through experimental design when Ar is used 1 Is selected as
One of them, ar 2 Is selected as
The structural formula of the prepared diamine monomer is as follows in sequence:
from the above structural formula analysis, it can be seen that: the PI thin film prepared by the above preferred monomer has excellent dielectric properties, because firstly Ar 1 、Ar 2 The aromatic heterocyclic structure has higher rigidity, the stacking degree between molecular chains in space is reduced, the content of heteroatoms such as nitrogen, oxygen and the like is higher, the polarity of nitrogen heteroatom can increase the acting force between the molecular chains, the free mobility of the chains is reduced, and higher thermal stability can be maintained. Finally, the hetero atom containing the lone pair of electrons may interact with the imide ring, which is beneficial to improving the electrical property of the polyimide film to a certain extent.
The invention develops a carbonyl-containing polysubstituted aromatic diamine monomer for preparing a transparent polyimide film with good solubility, flexibility, processability, higher tensile strength and lower dielectric loss property by designing a molecular structure, and the structure is designed because the practice discovers that the carbonyl can enhance the rigidity of a molecular chain under the conjugation effect of the carbonyl on benzene ring when the benzene ring in the middle of the diamine monomer contains the carbonyl, and simultaneously, the carbonyl is connected with large steric hindrance alkyl or aryl to have larger steric bulk, so the spatial arrangement between the molecular chain and the chain can be promoted to a certain degree, and the random motion of the chain segment can be inhibited. The carbonyl group can also generate stronger interaction with other atoms, the polyimide containing the carbonyl group can generate a crosslinking reaction, and the film after crosslinking and curing has higher thermal stability and higher thermal decomposition temperature, so that the product can be widely applied to synthesizing polyimide films with higher tensile strength and lower dielectric loss.
Through experiments, when Ar is 1 Is selected as
Ar 2 Is selected as
The performance of the prepared PI film is best.
The invention also provides a first preparation method of the carbonyl-containing polysubstituted aromatic diamine monomer, which mainly comprises the following steps:
will contain a substituent R 1 The p-aminophenol and the m-dihalogen benzene carbonyl compound are mixed with strong base and organic solvent to obtain a target product through reaction.
Preferably, the preparation method further comprises a method for post-treating the target product:
and settling, filtering, drying and recrystallizing the target product to obtain the white aromatic diamine monomer.
Preferably, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound is (3.1 to 5.0): 1.0.
preferably, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound is 4.0:1.0.
in addition to this, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound can also be 3.1: 1. 3.2: 1. 3.3: 1. 3.4: 1. 3.5: 1. 3.6: 1. 3.7: 1. 3.8: 1. 3.9: 1. 4.1: 1. 4.2: 1. 4.3: 1. 4.4: 1. 4.5: 1. 4.6: 1. 4.7: 1. 4.8: 1. 4.9:1, etc.
Preferably, the organic solvent is one or a combination of more of 1, 4-dioxane, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the organic solvent is 1, 4-dioxane and N, N-dimethylformamide according to the mass ratio of (3-6): (4-7) in proportion.
Preferably, the organic solvent is 1, 4-dioxane and N, N-dimethylformamide in a mass ratio of 4:6 in proportion.
Preferably, the mass ratio of the using amount of the organic solvent to the sum of the using amounts of the p-aminophenol and the m-dihalo-phenylcarbonyl compound is (2.0-4.0): 1.0.
preferably, the mass ratio of the amount of the organic solvent to the sum of the amounts of the p-aminophenol and the m-dihalobenzene carbonyl compound is 3.0:1.0.
besides, the mass ratio of the using amount of the organic solvent to the sum of the using amounts of the p-aminophenol and the m-dihalo-phenylcarbonyl compound can be 2.1: 1. 2.1: 1. 2.3: 1. 2.4: 1. 2.5: 1. 2.6: 1. 2.7: 1. 2.8: 1. 2.9: 1. 3.1: 1. 3.2: 1. 3.3: 1. 3.4: 1. 3.5: 1. 3.6: 1. 3.7: 1. 3.8: 1. 3.9:1, etc.
Preferably, the strong base is one or a combination of potassium carbonate, sodium carbonate, potassium phosphate, potassium hydroxide and sodium hydroxide.
Preferably, the strong base is potassium phosphate.
Preferably, the mass ratio of the using amount of the strong base to the using amount of the p-aminophenol is (1.0-3.0): 1.0.
preferably, the mass ratio of the amount of the strong base to the amount of the p-aminophenol is 2.0:1.0.
in addition, the mass ratio of the using amount of the strong base to the using amount of the p-aminophenol can be 1.1: 1. 1.2: 1. 1.3: 1. 1.4: 1. 1.5: 1. 1.6: 1. 1.7: 1. 1.8: 1. 1.9: 1. 2.1: 1. 2.1: 1. 2.3: 1. 2.4: 1. 2.5: 1. 2.6: 1. 2.7: 1. 2.8: 1. 2.9:1, etc.
Preferably, the reaction temperature is 81-130 ℃, and the reaction time is 9-14h.
Preferably, the reaction temperature is 100 ℃ and the reaction time is 10h.
In addition, the reaction temperature can be 81 degrees, 83 degrees, 85 degrees, 88 degrees, 89 degrees, 91 degrees, 92 degrees, 95 degrees, 98 degrees, 99 degrees, 102 degrees, 105 degrees, 108 degrees, 110 degrees, 112 degrees, 114 degrees, 118 degrees, 119 degrees, 120 degrees, 122 degrees, 124 degrees, 125 degrees, 127 degrees, 129 degrees C; the reaction time may also be 11h, 12h, 13h, etc.
Preferably, the solvent used for recrystallization is an alcohol/water system, and the alcohol is selected from one or a combination of more of methanol, ethanol, ethylene glycol, isopropanol, 1, 2-propylene glycol, n-butanol, 2-butanol or 1, 3-butanediol.
The invention also provides a second preparation method of the carbonyl-containing polysubstituted aromatic diamine monomer, which mainly comprises the following steps:
will contain a substituent R 1 The p-aminophenol, the m-dihalogen benzene carbonyl compound and the ionic liquid catalyst are mixed and reacted to obtain a target product.
Preferably, the preparation method further comprises a method of post-treating the target product:
and centrifuging the target product, washing, drying and recrystallizing the centrifuged solid to obtain the white aromatic diamine monomer.
Preferably, the speed of the centrifugation is 4000-6000rpm, and the time of the centrifugation is 20-40min.
Preferably, the rate of centrifugation is 5000rpm and the time of centrifugation is 30min.
Besides, the speed of the centrifugation can be 4200rpm, 4500rpm, 4800rpm, 5200rpm, 5700rpm, 5900rpm, and the like, and the time of the centrifugation can be 22min, 25min, 27min, 35min, 38min, 39min, and the like.
Preferably, the reaction temperature is 25-100 ℃, and the reaction time is 6-12h.
Preferably, the temperature of the reaction is 80 ℃ and the time of the reaction is 8h.
In addition, the reaction temperature can be 28 degrees C, 30 degrees C, 35 degrees C, 36 degrees C, 40 degrees C, 42 degrees C, 45 degrees C, 50 degrees C, 55 degrees C, 58 degrees C, 60 degrees C, 62 degrees C, 65 degrees C, 69 degrees C, 70 degrees C, 75 degrees C, 78 degrees C, 79 degrees C, 85 degrees C, 89 degrees C, 92 degrees C, 95 degrees C, 97 degrees C, 99 degrees C, the reaction time can also be 7 hours, 8 hours, 9 hours, 11 hours and so on.
Preferably, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound is (1.0-4.0): 1.0.
preferably, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound is 3.0:1.0.
in addition to this, the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound may also be 1.1: 1. 1.3: 1. 1.5: 1. 1.8: 1. 2.0:1. 2.1: 1. 2.2: 1. 2.5: 1. 2.7: 1. 2.9: 1. 3.1: 1. 3.2: 1. 3.3: 1. 3.4: 1. 3.5: 1. 3.6: 1. 3.7: 1. 3.8: 1. 3.9:1, etc.
Preferably, the ionic liquid catalyst is an imidazole ionic catalyst;
the imidazole ionic catalyst is one or a combination of several of the following catalysts:
preferably, the mass ratio of the amount of the ionic catalyst to the sum of the amounts of the para-aminophenol and the meta-dihalobenzene carbonyl compound is (2.0 to 4.0): 1.0.
preferably, the mass ratio of the amount of the ionic catalyst to the sum of the amounts of the p-aminophenol and the m-dihalobenzene carbonyl compound is 3.0:1.0.
in addition to this, the mass ratio of the amount of the ionic catalyst to the sum of the amounts of the p-aminophenol and the m-dihalobenzene carbonyl compound may also be 2.1: 1. 2.1: 1. 2.3: 1. 2.4: 1. 2.5: 1. 2.6: 1. 2.7: 1. 2.8: 1. 2.9: 1. 3.1: 1. 3.2: 1. 3.3: 1. 3.4: 1. 3.5: 1. 3.6: 1. 3.7: 1. 3.8: 1. 3.9:1, etc.
The imidazole ionic catalyst selected by the invention is a new catalytic medium in recent years, can replace the traditional strong base catalyst and organic solvent to be applied to organic reaction, has the advantages of environmental protection, low saturated steam pressure, good thermal stability and the like, and can reduce the damage to the environment and equipment when in use.
Preferably, the solvent used for recrystallization is an alcohol/water system, and the alcohol is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, 1, 2-propylene glycol, n-butanol, 2-butanol or 1, 3-butanediol.
Preferably, the chemical structural formula of the m-dihalobenzene carbonyl compound is:
It has been found through practice that the above mentioned parameters, such as the molar ratio between the raw materials, the reaction temperature, the reaction pressure, the dosage of the ionic liquid catalyst reagent, etc., need to be controlled within a relatively suitable range, which should not be too high or too low, because if the reaction temperature is too high and the reaction time is too long, on the one hand, resource waste is generated and it is not economical, on the other hand, many materials involved in the reaction cannot be guaranteed to react under the best activity condition, and if the temperature is too low, the reaction time is too short, and there are too many by-products, and the desired target product cannot be obtained, and also the molar ratio between the raw materials, in particular, needs to be controlled within a relatively suitable range, because if the dosage of the m-dihalobenzene carbonyl compound is too large or too small, too many by-products are generated, which is not favorable for the reaction to proceed.
For example, when the m-dihalophenylcarbonyl compound is reacted with a substituent R 1 Is less than 1.0:2.0 will generate a large amount of mono-substituted by-product a, when the molar ratio is higher than 1.0:4.0, a large amount of p-aminophenol remains, and when a polyimide film is produced using a monosubstituted monomer (by-product A), the apparent shape after film formation is yellow brittle fragments, film formation is impossible, and the difference from the expected thermal and mechanical properties is large, so that it is necessary to control the amount within a suitable molar ratio range, and similarly, when the reaction time is too short, or the temperature is too low, a large amount of the following by-product A is easily produced, and therefore by controlling suitable operating conditions, the reaction can be improvedOptionally, the structure of the monosubstituted by-product a is:
in conclusion, the by-product A of the above formula is not the target product of the reaction, so in order to ensure the purity of the target product prepared by the present invention, it is necessary to strictly ensure that the parameters of the above two preparation methods are kept within the range defined by the present invention, and the target product is prepared under the optimal operating conditions.
Compared with the prior art, the invention has at least the following advantages:
(1) The purity of the carbonyl-containing polysubstituted aromatic diamine monomer is more than 99.5 percent, and the carbonyl-containing asymmetric diamine structure is introduced, so that the polyimide with the asymmetric structure prepared by the method has good solubility, flexibility, processability, higher tensile strength and lower dielectric loss.
(2) The preparation method provided by the invention is simple to operate, the whole preparation method is low in energy consumption and cost, high-purity white solid can be obtained, the cost for preparing polyimide is greatly saved, and the preparation method is widely popularized and applied.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is the NMR chart of the diamine monomer provided in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art 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
(1) Under the protection of nitrogen, a three-neck flask with mechanical stirring is added with a mixture of a nitrogen gas and a nitrogen gas, wherein the molar ratio of the nitrogen gas to the nitrogen gas is 3.0:1.0 with substituents R 1 Further adding a proper amount of organic solvent and alkaline catalyst into the p-aminophenol A and the m-dihalogeno-phenylcarbonyl compound B respectively, stirring for half an hour at room temperature, heating to 100 ℃, reacting for 10 hours, and finishing the reaction.
(2) The white aromatic diamine monomer can be obtained after precipitation, filtration, drying and recrystallization.
Wherein, the organic solvent selected in the embodiment is 1, 4-dioxane and N, N-dimethylformamide according to the mass ratio of 4:6, the mass ratio of the dosage of the p-aminophenol to the dosage of the m-dihalogenophenylcarbonyl compound to the mass ratio of the p-aminophenol to the m-dihalogenophenylcarbonyl compound is 4.0:1.0; the alkaline catalyst is selected from potassium phosphate, and the mass ratio of the dosage of the potassium phosphate to the dosage of the p-aminophenol is 2.0:1.0; the alcohol used in the recrystallization is methanol; ar is 1 The selection is as follows:
ar is 2 Is selected as
The chemical structural formula of the obtained target product is as follows:
as shown in fig. 1, the specific characterization data is as follows:
1 H NMR(400MHz，DMSO-d 6 )δ8.0–7.8(m，2H)，7.7–7.6(m，1H)，7.6–7.5(m，2H)，7.3(t，J＝8.4Hz，1H)，6.7–6.6(m，4H)，6.6–6.5(m，4H)，6.4(d，J＝8.4Hz，2H)，5.0(s，4H)。
examples 2 to 9
The specific implementation manner is the same as that of example 1, except that the reaction temperature, the reaction time and the molar ratio of the raw materials are slightly different, and the specific setting parameters and the purity of the target product are specifically shown in table 1.
Example 10
(1) Under the protection of ammonia gas, adding a mixture of 3.0:1.0 with substituents R 1 The p-aminophenol A and the m-dihalo benzene carbonyl compound B are further added with an ionic liquid catalyst respectively, stirred for half an hour at room temperature, heated to 80 ℃ and reacted for 10 hours, and then the reaction is finished.
(2) And centrifuging a product obtained by the reaction, washing, drying and recrystallizing a solid obtained by centrifuging to obtain a white aromatic diamine monomer.
Wherein the rotation speed of centrifugation is 5000rpm, the time of centrifugation is 30min, the selected ionic catalyst is ionic catalyst 1, and the structural formula of the ionic catalyst 1 is shown in the specification
The mass ratio of the dosage of the p-aminophenol to the dosage of the m-dihalogenophenylcarbonyl compound to the sum of the dosages of the p-aminophenol and the m-dihalophenylcarbonyl compound is 3.0:1.0; the alcohol used in the recrystallization is methanol; ar (Ar) 1 The selection is as follows:
Ar 2 is selected as
The chemical structural formula of the obtained target product is as follows:
examples 11 to 18
The specific implementation manner is the same as that of example 1, except that the reaction temperature, the reaction time and the molar ratio of the raw materials are slightly different, and the specific setting parameters and the purity of the target product are specifically shown in table 2.
TABLE 1 Effect of reaction conditions on the reaction
By analyzing the data in table 1, the molar ratio between the raw materials, the reaction temperature, the reaction pressure, the amount of the ionic liquid catalyst reagent used, and the like need to be controlled within relatively suitable ranges. As in example 4, when the molar ratio between the starting materials is 3:1 hour and the reaction temperature is only 40 ℃, the content of the target product is only 12 percent, 88 percent of by-products are generated, and the reaction efficiency is greatly reduced. The reaction temperature is also strictly controlled, and if the temperature is too high, as in example 3 and example 5, the temperature rises to 140 ℃, and more by-products are produced.
TABLE 2 Effect of reaction conditions on the reaction
Note: the by-product contents listed in Table 1-2 refer to the content of by-product A; the content of the by-products and the content of the target products are detected by a gas chromatograph, the amount of the detected substance (i) is in direct proportion to the peak area of the detected substance on a chromatogram: mi = fi × Ai, fi being a quantitative correction factor.
Experimental example 1
Based on example 1 as group 1, the units of the other groups were prepared in the same way, except that different Ar's were selected 1 、Ar 2 Then, polyimide films prepared from the diamine monomers were measured at room temperature and 25 ℃ to obtain a thickness of 30 μm, and the results are shown in tables 3 and 4.
TABLE 3 Ar 1 、Ar 2 Influence on the structural formula of diamine monomer
TABLE 4 Ar 1 、Ar 2 Effect on polyimide Properties
By analyzing the dielectric constant, dielectric loss and tensile strength of the PI films prepared in the above groups 1-10 and comparative examples 1-2, it can be seen that: by analyzing the dielectric constant, dielectric loss and tensile strength of the PI films prepared in the above examples 1-10 and comparative examples 1-2, it can be seen that when the benzene ring in the middle of the diamine monomer contains carbonyl, the carbonyl can enhance the rigidity of the molecular chain due to the conjugation effect of the carbonyl on the benzene ring, and at the same time, the carbonyl has a larger space volume due to the steric hindrance alkyl or aryl connected with the carbonyl, which can promote the spatial arrangement between the molecular chain and the chain, and inhibit the random movement of the chain segment. In comparative examples 1 and 2, the two structures do not adopt the monomer substituent group of the invention, and are only common diamine monomers, so that the rigidity of a molecular chain is weaker in the polymerization process of the monomers, the conjugation and space effects of carbonyl on benzene rings are lacked, the molecular chain can generate random motion, and the parameters such as the mechanical property, the dielectric constant and the like expressed by the two structures are poorer than those of the monomer of the invention. Therefore, the polyimide film prepared by the monomer prepared by the invention has lower dielectric constant, extremely low dielectric loss and higher tensile strength.
Firstly, the invention designs the synthesis of the monomer structure containing carbonyl meta-substituted diamine; secondly, the invention adopts two synthesis modes, one is a conventional alkali catalysis mode, and the other is a completely new ionic liquid catalysis monomer synthesis method, thereby avoiding the residue of metal cations such as potassium ions, sodium ions and the like when inorganic alkali is adopted. Because trace amount of metal ions remained in the polyimide film also resulted in high dielectric loss. Finally, the content of impurities or byproducts in the monomers greatly influences the performance of the subsequent polymerization process and the film. The monomer prepared by the method has high purity which is more than 99.5 percent and is white solid, and provides great purity advantage for subsequent preparation of film, thereby preparing a series of polyimide films with low dielectric constant and dielectric loss.
Finally, it is to be understood that the above embodiments are merely exemplary embodiments employed to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention, and these changes and modifications are to be considered as within the scope of the invention.
Claims (10)
1. The carbonyl-containing polysubstituted aromatic diamine monomer is characterized by having a structural formula as follows:
2. the method for preparing a carbonyl group-containing polysubstituted aromatic diamine monomer according to claim 1, comprising the steps of:
will contain a substituent R 1 Mixing the p-aminophenol, the m-dihalogeno-benzene carbonyl compound and an ionic liquid catalyst for reaction to obtain a target product;
the chemical structural formula of the m-dihalobenzene carbonyl compound is as follows:
wherein, R is 1 The p-aminophenol, the Ar 2 Corresponding to the structure of claim 1;
the ionic liquid catalyst is an imidazole ionic catalyst;
the imidazole ionic catalyst is one or a combination of several of the following catalysts:
3. the method according to claim 2, wherein the reaction temperature is 25 to 100 ℃ and the reaction time is 6 to 12 hours.
4. The production method according to claim 2, characterized in that the molar ratio of the p-aminophenol to the m-dihalobenzene carbonyl compound is (1.0 to 4.0): 1.0.
5. the production method according to claim 2, characterized in that the mass ratio of the amount of the ionic catalyst to the sum of the amounts of the p-aminophenol and the m-dihalophenylcarbonyl compound is (2.0-4.0): 1.0.
6. the method for preparing a carbonyl group-containing polysubstituted aromatic diamine monomer according to claim 1, comprising the steps of:
will contain a substituent R 1 Mixing the p-aminophenol and the m-dihalobenzene carbonyl compound with strong base and an organic solvent, and reacting to obtain a target product;
the chemical structural formula of the m-dihalobenzene carbonyl compound is as follows:
wherein, R is 1 The p-aminophenol, the Ar 2 Corresponding to the structure of claim 1.
7. The method according to claim 6, wherein the molar ratio of the p-aminophenol to the m-dihalobenzenecarbonyl compound is (3.1 to 5.0): 1.0.
8. the preparation method according to claim 6, wherein the organic solvent is one or more of 1, 4-dioxane, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the mass ratio of the using amount of the organic solvent to the using amount and the mass ratio of the p-aminophenol and the m-dihalobenzene carbonyl compound are (2.0-4.0): 1.0.
9. the preparation method of claim 6, wherein the strong base is one or more of potassium carbonate, sodium carbonate, potassium phosphate, potassium hydroxide and sodium hydroxide;
the mass ratio of the using amount of the strong base to the using amount of the p-aminophenol is (1.0-3.0): 1.0.
10. the method according to claim 6, wherein the reaction temperature is 81-130 ℃ and the reaction time is 9-14h.
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| CN103073702A (en) * | 2013-01-23 | 2013-05-01 | 中国科学技术大学 | Polyimide with sulfonated side chain and preparation method thereof |
| CN109942817A (en) * | 2019-03-21 | 2019-06-28 | 深圳先进技术研究院 | A kind of polyimide precursor, preparation method and resin combination and its application |
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| CN103073702A (en) * | 2013-01-23 | 2013-05-01 | 中国科学技术大学 | Polyimide with sulfonated side chain and preparation method thereof |
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