CN114456090A - Cyanogen-containing polysubstituted aromatic diamine monomer and preparation method thereof - Google Patents

Cyanogen-containing polysubstituted aromatic diamine monomer and preparation method thereof Download PDF

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CN114456090A
CN114456090A CN202210173343.2A CN202210173343A CN114456090A CN 114456090 A CN114456090 A CN 114456090A CN 202210173343 A CN202210173343 A CN 202210173343A CN 114456090 A CN114456090 A CN 114456090A
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diamine monomer
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aromatic diamine
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CN114456090B (en
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谢劲
夏嗣禹
朱成建
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Nanjing University
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Abstract

The invention provides a cyanogen-containing poly-substituted aromatic diamine monomer, which has a structural formula as follows:
Figure DDA0003519423260000011
wherein R is1、R2is-H, -CF3、‑OCH3Or one of alkyl groups. The diamine monomer can be applied to the preparation of high-performance polyimide film materials, and can further improve the potential application values of the prepared polyimide film materials such as dissolution film-forming property, optical transparency, tensile strength property, dielectric loss property and the like.

Description

Cyanogen-containing poly-substituted aromatic diamine monomer and preparation method thereof
Technical Field
The invention relates to a diamine monomer and the preparation field thereof, in particular to a cyanogen-containing poly-substituted aromatic diamine monomer and a preparation method thereof.
Background
Polyimide is a high-end polymer material with excellent performance and is widely applied in the high-tech field. The high-rigidity high-temperature-resistant high-performance silicon-based composite material contains a strong-rigidity benzene ring and an imide ring, has excellent high-temperature resistance, mechanical performance, corrosion resistance and electrical performance, and is widely applied to the new technical fields of aerospace, electronic devices, precision machinery, high-performance packaging, microelectronics and the like. The development of photoelectric devices in the future gradually shows the trend of light weight, large size, ultra-thin and flexibility, and the flexible polymer material has become the first choice of flexible photoelectric packaging substrate materials in the future due to the advantages of light weight, high impact resistance and the like.
However, the common polyimide has very poor melt processability and solubility, so that the popularization and the application of the common polyimide in the civil field are limited. In the process of synthesizing diamine monomers, inorganic strong base is mostly added to synthesize the monomers at present, but in the industrial production process, the addition of a large amount of inorganic base can cause corrosion of mechanical equipment, and can emit huge heat in the reaction process, so that the control is difficult, certain dangerousness is realized, and meanwhile, environmental pollution can be caused. The diamine monomer product synthesized by the method does not adopt inorganic base and has no metal ion residue, and a series of high-purity diamine monomers are prepared. The apparent property and the electrical property of the polyimide film prepared by using the monomer are greatly improved, and the demand of high-purity electronic chemicals can be met.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention provides a cyano-containing poly-substituted aromatic diamine monomer, which is a novel cyano-containing poly-substituted aromatic diamine monomer structure, wherein a cyano-group asymmetric diamine structure is introduced, and different functional groups are introduced into a molecular chain of a polymer from the structure.
The second purpose of the invention is to provide the preparation method of the cyano-containing poly-substituted aromatic diamine monomer, the preparation method adopts a green synthesis method of a basic ionic liquid catalyst for the first time, no strong base additive needs to be additionally introduced, the ionic liquid is used as a catalyst and a solvent, meanwhile, the preparation method has mild reaction conditions and high yield, can realize the recycling of the ionic liquid catalyst, is convenient to recover, avoids the characteristics of waste and pollution caused by using the traditional strong base, meets the synthesis requirement of green environmental protection, obtains the monomer as brown or black solid powder in the current industrial production, and finally can prepare the colorless or light yellow diamine monomer with the purity of more than 99.5 percent by adopting the preparation method. The whole preparation method has low energy consumption, low cost and 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 cyanogen-containing poly-substituted aromatic diamine monomer, which has a structural formula as follows:
Figure BDA0003519423240000021
wherein R is1、R2is-H, -CF3、-OCH3Or one of the alkyl radicals, Ar1、Ar2Is an aromatic ring or an aromatic heterocyclic ring.
Preferably, Ar1、Ar2Is one of the following groups, wherein the substitution positions of the same aromatic ring are different:
Figure BDA0003519423240000022
Figure BDA0003519423240000031
preferably, when Ar is1Is selected as
Figure BDA0003519423240000032
Ar2Is selected as
Figure BDA0003519423240000033
Figure BDA0003519423240000034
One of them, wherein, Ar1Can have m-methoxy substituent and m-methyl substituent, and the structural formula of the prepared diamine monomer is as follows:
Figure BDA0003519423240000035
preferably, in order to obtain the polyimide film with excellent dielectric constant, dielectric loss and other properties, the polyimide film is optimized through experimental design when Ar2Is selected as
Figure BDA0003519423240000036
When is, Ar1Is selected as
Figure BDA0003519423240000037
Figure BDA0003519423240000038
One of the diamine monomers is prepared by the following steps:
Figure BDA0003519423240000039
Figure BDA0003519423240000041
the PI film prepared by structurally analyzing the preferred monomers has excellent dielectric properties: first Ar1，Ar2The 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 therefore 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 cyano-containing poly-substituted aromatic diamine monomer for preparing a transparent polyimide film by designing a molecular structure, and the cyano-containing poly-substituted aromatic diamine monomer is designed into the structure, has good solubility, flexibility, processability, higher tensile strength and lower dielectric loss, and is characterized in that when a benzene ring in the middle of the diamine monomer has a cyano group, the cyano group has a triple bond structure, and in the process of some chemical reactions, the cyano group can generate stronger interaction with other atoms, the cyano-containing polyimide generates a crosslinking reaction, and the film after crosslinking and curing shows 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 experimental verification, when Ar is1Is selected as
Figure BDA0003519423240000042
Ar2Is selected as
Figure BDA0003519423240000043
And the prepared PI film has the best performance.
The invention also provides a preparation method of the monomer besides providing the structural formula of the cyanogen-containing poly-substituted aromatic diamine monomer, which comprises the following steps:
will bear a substituent R1The p-aminophenol and the m-dihalobenzene compound react with an ionic liquid catalyst to obtain a target product.
The invention adopts the green synthesis method of the alkaline ionic liquid catalyst for the first time, does not need to additionally add a strong base additive, has mild reaction conditions and high yield, can realize the recycling of the ionic liquid catalyst, and meets the synthesis requirement of green environmental protection.
Preferably, the ionic liquid catalyst after reaction can be recycled after reduced pressure distillation.
Preferably, the m-dihalobenzene compound has the structural formula:
Figure BDA0003519423240000051
wherein, the halogen X substituent is one or more of Cl, Br and I.
Preferably, said substituent R is1The molar ratio of the p-aminophenol to the m-dihalobenzene compound of (1.0-4.0): 1.0.
in addition, the molar ratio of the p-aminophenol of the substituent R1 to the m-dihalobenzene compound may 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, 3.0:1, 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, and the like.
Preferably, the temperature of the reaction is from 25 ℃ to 100 ℃.
In addition, the reaction temperature can be 28 degrees, 30 degrees, 35 degrees, 36 degrees, 40 degrees, 42 degrees, 45 degrees, 50 degrees, 55 degrees, 58 degrees, 60 degrees, 62 degrees, 65 degrees, 69 degrees, 70 degrees, 75 degrees, 78 degrees, 79 degrees, 85 degrees, 89 degrees, 92 degrees, 95 degrees, 97 degrees, 99 degrees C.
Preferably, the reaction time is 6h to 12 h.
Besides, the reaction time may be 7h, 8h, 9h, 11h, and the like.
Preferably, the ionic liquid catalyst is an imidazole ionic catalyst.
The imidazole ionic catalyst adopted by the invention is used as a new catalytic medium in recent years, has the advantages of environmental protection, low saturated steam pressure, good thermal stability and the like, can replace the traditional alkali and organic solvent to be applied to organic reaction, and reduces the corrosion to equipment and the pollution to the environment.
Preferably, the imidazole ionic catalyst is selected from one or more of the following catalysts:
Figure BDA0003519423240000052
preferably, the preparation method further comprises a method for post-treating the target product:
centrifuging the target product, and washing, drying and recrystallizing the centrifuged solid to obtain a white aromatic diamine monomer;
preferably, the speed of the centrifugation is 4000-6000rpm, and the time of the centrifugation is 20-40 min.
Preferably, the rate of centrifugation is 5000rpm, and the practice of centrifugation is 30 min.
In addition, the centrifugation rate can be 4200rpm, 4500rpm, 4800rpm, 5200rpm, 5700rpm, 5900rpm, etc., and the centrifugation time can be 22min, 25min, 27min, 35min, 38min, 39min, etc.
Preferably, the centrifuged liquid is washed by water, the salt dissolved in water is removed, and then the centrifuged liquid is dried and distilled to obtain pure ionic liquid which can be recycled.
Preferably, the solvent used for recrystallization is an alcohol/water mixture;
wherein 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.
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 and the reaction time are too long and not economical, the reaction can not be carried out under the best activity condition, and if the reaction temperature and the reaction time are too short, the reaction time will be too long, and the by-products will be too much to obtain the target product, and the same, especially the molar ratio between the raw materials, needs to be controlled within a relatively suitable range, because if the dosage of the dihalobenzonitrile compound B is too large or too small, too many by-products will be produced, which is not good for the reaction. The possible mechanism is presumed to be:
Figure BDA0003519423240000061
for example, when dihalobenzonitrile compound B is reacted with a compound containing a substituent R1When the molar ratio of the p-aminophenol A is lower than 1.0:2.0, a large amount of monosubstituted by-product A is generated, when the molar ratio is higher than 1.0:4.0, a large amount of raw material A is remained, when a polyimide film is prepared by adopting a monosubstituted monomer (the by-product A), the apparent shape of the film is yellow brittle fragments, the film cannot be formed, and the difference from the expected required thermal property and mechanical property is large, so that the control in an appropriate molar ratio range is necessary, 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 generated, so the reaction selectivity can be improved by controlling appropriate operating conditions, and the monosubstituted by-product A has the structure:
Figure BDA0003519423240000071
in short, the by-product a in the above structural formula is not a target product of the reaction, so in order to control the purity of the obtained target product, many parameters involved in the whole preparation method are searched, and the preparation is performed while maintaining the optimum operating conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the purity of the cyano-containing poly-substituted aromatic diamine monomer is more than 99.5%, a cyano-group asymmetric diamine structure is introduced, and the asymmetric structure polyimide prepared by the method has good solubility, flexibility, processability, higher tensile strength and lower dielectric loss.
(2) The monomer preparation method disclosed by the invention is low in temperature, does not need an extra strong base additive, can realize the recycling of the ionic liquid catalyst, meets the synthesis requirement of environmental protection, is low in energy consumption and cost, can obtain high-purity white or light yellow solid, and is worthy of wide popularization and application.
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Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a nuclear magnetic resonance carbon spectrum of a diamine monomer provided in example 1;
FIG. 2 is a NMR spectrum of a diamine monomer provided in example 1;
FIG. 3 is a NMR spectrum of a diamine monomer provided in example 8;
FIG. 4 is a NMR spectrum of a diamine monomer provided in example 8;
FIG. 5 is a NMR spectrum of a diamine monomer provided in example 9;
FIG. 6 is a NMR spectrum of a diamine monomer provided in example 9;
FIG. 7 is a NMR spectrum of a diamine monomer provided in example 10;
FIG. 8 is a NMR spectrum of a diamine monomer provided in example 10.
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) Adding substituent R with a molar ratio of 2:1 into a three-neck flask with mechanical stirring under the protection of nitrogen1The p-aminophenol A and the dihalo benzonitrile compound B are further respectively subjected to ionic liquid catalyst stirring for half an hour at room temperature, then the temperature is raised to 65 ℃ for reaction for 10 hours, and the reaction is finished;
(2) obtaining white diamine monomer after settling, filtering, drying and recrystallizing;
in the above reaction, the ionic liquid catalyst is ionic liquid catalyst 1, and the structural formula of the ionic catalyst is as follows:
Figure BDA0003519423240000081
in an amount containing the substituent R12 times of the sum of the mass of the p-aminophenol A and the dihalo-benzonitrile compound B, Ar1The selection is as follows:
Figure BDA0003519423240000082
Ar2the selection is as follows:
Figure BDA0003519423240000083
the chemical structural formula of the obtained target product is as follows:
Figure BDA0003519423240000091
the specific characterization data are as follows:
as shown in figure 1 of the drawings, in which,13c NMR (101MHz, DMSO-d6) delta 162.1,144.7,141.8,135.4,127.0,122.6,120.4,116.1,113.6,106.7,90.3,16.9,15.3 carbon spectra were consistent with the expected product spectra structure.
As shown in the figureAs shown in figure 2, the first and second,1h NMR (400MHz, DMSO-d6) δ 7.33(t, J ═ 8.5Hz,1H),6.75(s,2H),6.55(s,2H),6.16(d, J ═ 8.5Hz,2H),4.83(s,4H),2.03(s,6H),1.97(s,6H). the hydrogen spectrum is consistent with the expected product spectrum structure.
The specific characterization data of the high resolution mass spectrum are as follows: HRMS (ESI) calcd for C23H23O2N3[M+H]+374.1863; found 374.1839. high resolution mass spectrometry is consistent with the expected product pattern structure, and the specific detection data is shown in table 1.
Examples 2 to 7
The specific process is the same as example 1, except that the reaction temperature, reaction time and molar ratio of the raw materials are slightly different, and the specific setting parameters and purity of the target product are specifically shown in table 1.
Example 8
The specific method is the same as example 1, except that as shown in table 1, the ionic liquid catalyst is ionic liquid catalyst 4, and the structural formula of the ionic liquid catalyst 4 is as follows:
Figure BDA0003519423240000092
in an amount to contain the substituent R1The mass sum of the p-aminophenol A and the dihalo benzonitrile compound B is 2 times, and the chemical structural formula of the obtained target product is as follows:
Figure BDA0003519423240000101
the specific characterization data are as follows:
as shown in figure 3 of the drawings,13C NMR(101MHz,DMSO-d6) Delta 162.4,144.5,143.9,135.2,122.8,122.1,118.7,114.7,113.7,107.8,91.5,17.4. the carbon spectrum is consistent with the expected product spectrum structure.
As shown in figure 4 of the drawings,1HNMR(400MHz,DMSO-d6) δ 7.36(t, J ═ 8.5Hz,1H), 6.83-6.81 (m,2H), 6.78-6.75 (m,2H), 6.69-6.67 (m,2H),6.31(d, J ═ 8.5Hz,2H),4.89(s,4H) hydrogen spectra were consistent with the expected product spectra structure.
The specific characterization data of the high resolution mass spectrum are as follows: HRMS (ESI) calcd forC21H19O2N3[M+H]+346.1550; found 346.1529. high resolution mass spectrometry is consistent with the expected product pattern structure.
Example 9
The specific method is the same as that of example 1, except that as shown in table 1, the ionic liquid catalyst is ionic liquid catalyst 5, and the structural formula of the ionic liquid catalyst 5 is:
Figure BDA0003519423240000102
in an amount to contain the substituent R1The mass sum of the p-aminophenol A and the dihalo benzonitrile compound B is 2 times, and the chemical structural formula of the obtained target product is as follows:
Figure BDA0003519423240000103
the specific characterization data are as follows:
as shown in figure 5 of the drawings,13C NMR(101MHz,DMSO-d6) Delta 161.2,152.4,148.9,135.5,127.1,113.4,112.9,111.6,108.0,91.5,9.8. the carbon spectrum is consistent with the expected product spectrum structure.
As shown in figure 6 of the drawings,1h NMR (400MHz, DMSO-d6) δ 7.39(t, J ═ 8.5Hz,1H),6.97(t, J ═ 8.0Hz,2H), 6.59-6.57 (m,2H), 6.34-6.28 (m,2H),6.26(d, J ═ 8.5Hz,2H),5.18(s,4H),1.90(s,6H) hydrogen spectra were consistent with the expected product spectra structures.
The specific characterization data of the high resolution mass spectrum are as follows: HRMS (ESI) calcd for C21H19O2N3[M+H]+346.1550; found 346.1528. high resolution mass spectrometry is consistent with the expected product pattern structure.
Example 10
The specific method is the same as example 1, except that as shown in table 1, the ionic liquid catalyst is ionic liquid catalyst 3, and the structural formula of the ionic liquid catalyst 3 is as follows:
Figure BDA0003519423240000111
in an amount containing the substituent R1P-aminophenol A and dihalobenzene ofThe mass sum of the nitrile compound B is 2 times, and the chemical structural formula of the obtained target product is as follows:
Figure BDA0003519423240000112
the specific characterization data are as follows:
as shown in figure 7 of the drawings,13c NMR (101MHz, DMSO). delta. 162.4,151.6,148.2,134.9,131.6,122.9,113.8,106.2,105.7,99.1,89.9,55.3. carbon spectra are consistent with the expected product spectra structure.
As shown in figure 8 of the drawings,1H NMR(400MHz,DMSO-d6)δ7.29(t,J＝8.5Hz,1H),6.85(d,J＝8.5Hz,2H),6.40(d,J＝2.4Hz,2H),6.20–6.18(m,2H),6.15(d,J＝8.5
hz,2H),5.19(s,4H),3.66(s,6H) hydrogen spectra are consistent with the expected product spectra structure.
The specific characterization data of the high resolution mass spectrum are as follows: HRMS (ESI) calcd for C19H19O4N3[M+H]+:
378.1448, respectively; found 378.1438. high resolution mass spectrometry is consistent with the expected product pattern structure.
TABLE 1 influence of reaction temperature, reaction time and molar ratio of raw materials on the reaction
Figure BDA0003519423240000113
Figure BDA0003519423240000121
Note: the by-product contents listed in the table refer to the content of by-product A;
the content of the by-product and the content of the target product 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 map, mi＝fi×Ai,fiIs a quantitative correction factor.
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 8, when the molar ratio between the starting materials is 2: 2, a large amount of by-products are produced, greatly reducing the efficiency of the reaction. And the reaction temperature is also strictly controlled, such as example 1 and example 6, the reaction temperature is only reduced from 65 ℃ to 25 ℃, and the content of the target product is reduced from 99% to 92%.
Experimental example 1
Based on example 1 as group 1, the preparation of the other monomers was identical except that different Ar's were selected1、Ar2Then, the prepared diamine monomer is prepared into a polyimide film, and the polyimide film is detected at room temperature of 25 ℃, and the thickness of the polyimide film is 30 mu m.
TABLE 2Ar1、Ar2Influence on the formula of diamine monomer
Figure BDA0003519423240000122
Figure BDA0003519423240000131
Figure BDA0003519423240000141
TABLE 3Ar1、Ar2Effect on polyimide film Properties
Group of Dielectric constant (10GHz) Dielectric loss (10GHz) Tensile Strength (MPa)
1 3.196 0.00204 170
2 3.214 0.00247 165
3 3.217 0.00225 158
4 3.870 0.00374 120
5 3.339 0.00278 134
6 3.313 0.00299 155
7 3.996 0.00364 157
8 3.256 0.00243 129
9 3.593 0.00388 133
10 3.661 0.00428 120
Comparative example 1 4.625 0.00798 90
Comparative example 2 4.312 0.00693 102
By analyzing the dielectric constant, dielectric loss and tensile strength of the PI films prepared in the groups 1-10 and the comparative examples 1-2, the polyimide films prepared by the monomer prepared by the invention have lower dielectric constant, extremely low dielectric loss and higher tensile strength. The invention firstly designs the synthesis of the monomer structure of the meta-substituted diamine, and the practice shows that when a benzene ring in the middle of a diamine monomer has a cyano group, the cyano group has a triple bond structure, the cyano group can generate stronger interaction with other atoms in the process of some chemical reactions, the polyimide containing the cyano group generates a crosslinking reaction, and the film after crosslinking and curing shows higher thermal stability and has higher thermal decomposition temperature, so that the product can be widely applied to the synthesis of polyimide films with higher tensile strength and lower dielectric loss. In comparative examples 1 and 2, the structure of the invention is not adopted, and only the common diamine monomer is adopted, so that the rigidity of the molecular chain is weaker in the polymerization process of the monomer, the spatial arrangement disorder can generate random motion at the same time, and the parameters such as the mechanical property, the dielectric constant and the like expressed by the monomer are poorer than those of the structural monomer of the invention.
Secondly, the invention adopts a novel method for synthesizing the monomer by catalyzing the ionic liquid, and avoids 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 taken to illustrate the principles of the present invention, which is not intended to be limiting. 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. A cyanogen-containing poly-substituted aromatic diamine monomer is characterized in that the cyanogen-containing poly-substituted aromatic diamine monomer has a structural formula as follows:
Figure FDA0003519423230000011
wherein R is1、R2is-H, -CF3、-OCH3Or one of the alkyl radicals, Ar1、Ar2Is an aromatic ring or an aromatic heterocyclic ring;
Ar1、Ar2is one of the following groups, wherein the substitution positions of the same aromatic ring are different:
Figure FDA0003519423230000012
preferably, when Ar is1Is selected as
Figure FDA0003519423230000013
Ar2Is selected as
Figure FDA0003519423230000014
Figure FDA0003519423230000015
One of them;
when Ar is2Is selected as
Figure FDA0003519423230000016
When is, Ar1Is selected as
Figure FDA0003519423230000017
One of them.
2. The method of claim 1, comprising the steps of:
will bear a substituent R1The p-aminophenol, the m-dihalobenzene compound and the ionic liquid catalyst are reacted to obtain a target product.
3. The method of claim 2, wherein the m-dihalobenzene compound has the structural formula:
Figure FDA0003519423230000021
wherein, the halogen X substituent is one or more of Cl, Br and I.
4. The process according to claim 2, wherein the substituent R is1The molar ratio of the p-aminophenol to the m-dihalobenzene compound of (1.0-4.0): 1.0.
5. the method of claim 2, wherein the reaction temperature is from 25 ℃ to 100 ℃.
6. The method according to claim 2, wherein the reaction time is 6 to 12 hours.
7. The preparation method according to claim 2, wherein the ionic liquid catalyst is an imidazole-based ionic catalyst.
8. The preparation method according to claim 7, characterized in that the imidazole ion catalyst is selected from one or more of the following catalysts:
Figure FDA0003519423230000022
9. the method according to claim 2, further comprising a step of post-treating the target product:
centrifuging the target product, and washing, drying and recrystallizing the centrifuged solid to obtain a white aromatic diamine monomer;
preferably, the speed of the centrifugation is 4000-6000rpm, and the time of the centrifugation is 20-40 min.
10. The method according to claim 9, wherein the solvent used for recrystallization is an alcohol/water mixture;
wherein 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.
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