CN111187187A - Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer - Google Patents
Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer Download PDFInfo
- Publication number
- CN111187187A CN111187187A CN202010154323.1A CN202010154323A CN111187187A CN 111187187 A CN111187187 A CN 111187187A CN 202010154323 A CN202010154323 A CN 202010154323A CN 111187187 A CN111187187 A CN 111187187A
- Authority
- CN
- China
- Prior art keywords
- hexafluoropropane
- bis
- phenyl
- solvent
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer. The novel sulfone-containing fluorine-containing diamine monomer is synthesized by taking hexafluorobisphenol A, N, N-dimethyl sulfo-acyl chloride as a raw material through six steps of organic reaction design: 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane. The method has the advantages of easily available raw materials, controllable reaction temperature, high yield and high purity. The prepared diamine monomer 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane can be used as a novel diamine monomer to react with some dianhydride to obtain a series of novel fluorine-containing sulfonyl-containing high-performance and functional polymers such as novel polyamide, polyimide, polyamideimide and the like. Particularly, the novel polyimide obtained by the reaction of the diamine monomer and the dianhydride has excellent heat resistance, mechanical properties, and excellent optical properties and solubility due to the introduction of fluorine and sulfone groups.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer.
Background
Polyimide materials are widely applied to the high-tech fields of aerospace, machinery, electronics, automobiles and the like due to excellent thermal stability, mechanical property, dielectric property, chemical resistance, corrosion resistance and the like. Due to the unique rigid main chain structure of polyimide, most of polyimides have the defects of higher processing temperature, insolubility, infusibility, poor processability and the like, thereby further limiting the wide application of the polyimides in related fields. In order to meet the development requirements of the modern high-tech field and overcome the defects of polyimide materials, the prepared polyimide materials with good solubility and excellent comprehensive performance are more and more interesting to researchers.
In recent years, there has been an increasing research for developing materials of novel structures by introducing chemical modification of specific groups or creating new frameworks. The design and synthesis of the novel diamine monomer play a crucial role in the design and modification of polyimide. Because fluorine atoms have higher electrical property, dielectric property and hydrophobic property, and because of the steric hindrance effect of fluorine groups, the solubility and the optical property of the fluorine-containing polymer can be effectively improved. Meanwhile, the strong polarity of the sulfonyl group can endow the polymer with high thermal stability and high wear resistance.
The invention provides a novel fluorine-containing sulfonyl-containing diamine 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane and a preparation method thereof, technically provides a synthesis method for preparing a novel diamine monomer, the novel monomer can be used for polymerizing to obtain polyimide, the polyimide effectively improves the solubility, optical property, hydrophobic property and wear resistance of the polyimide on the basis of maintaining thermal stability, and provides a raw material for preparing a polymer film which is comprehensive and excellent in new properties.
Disclosure of Invention
The invention aims to provide a preparation method of a 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer.
The idea of the invention is as follows: the novel sulfone-containing fluorine-containing diamine monomer is initially synthesized by taking hexafluorobisphenol A, N, N-dimethyl sulfo-acyl chloride as a raw material through six steps of organic reaction design: 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane.
The method comprises the following specific steps:
(1) weighing alkali, N-dimethylthio acyl chloride and bisphenol A according to a molar ratio of 2-2.2: 1, and weighing an organic solvent according to a mass-volume ratio of the bisphenol A to the organic solvent of 1 g: 3-5 mL; under the protection of nitrogen, dissolving alkali by using an organic solvent, adding bisphenol A, stirring in an ice bath at 0 ℃ for 0.5 h, adding N, N-dimethylthio acyl chloride, and stirring at 0-5 ℃ for reacting for 4-6 h. After the reaction, suction filtration was carried out using CH with a volume ratio of ice of 1:13OH/H2Washing with O solution for 4-5 times, drying at 80-100 ℃ overnight, and recrystallizing to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethylthioacyl hydroxyphenyl]And (3) hexafluoropropane.
(2) Heating the 2, 2-bis [4-N, N-dimethylthioacyl hydroxyphenyl ] hexafluoropropane prepared in the step (1) to 100-120 ℃ for reaction for 1-2 h, reacting at 200-220 ℃ for 1-2 h, reacting at 240-280 ℃ for 2-3 h, cooling to room temperature, adding dichloromethane to dissolve the product, performing rotary evaporation, performing vacuum drying at 30-50 ℃, and then recrystallizing to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane.
(3) Dissolving the 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane prepared in the step (2) and alkali in a molar ratio of 1: 1.0-1.2 in a solvent, wherein the volume mass ratio of the solvent to the 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane is 4-10 mL:1g, heating and refluxing for 10-15 h under the protection of nitrogen, cooling, acidifying, filtering, and recrystallizing to obtain the 2, 2-bis [ 4-mercaptophenyl ] hexafluoropropane.
(4) Dissolving the 2, 2-bis (4-mercaptophenyl) hexafluoropropane and 4-chloronitrobenzene prepared in the step (3) in a solvent according to a molar ratio of 1: 2.0-2.2, simultaneously adding alkali, wherein the molar ratio of the alkali to the 2, 2-bis (4-mercaptophenyl) hexafluoropropane is 2-3: 1, the mass-to-volume ratio of the solvent to the 2, 2-bis (4-mercaptophenyl) hexafluoropropane is 1 g: 10-15 mL, heating to a stable reflux state, reacting for 10-15 h, cooling, filtering, and recrystallizing to obtain the 2, 2-bis [4- (4-nitrobenzenethiophenyl) phenyl ] hexafluoropropane.
(5) Oxidizing the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane prepared in the step (4) into 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane by using a solvent, wherein the molar volume ratio of the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane to the solvent is 1: 10-15 mL, heating to a reflux temperature, reacting for 3-8 h, cooling, filtering, and recrystallizing to obtain the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane.
(6) Dissolving the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane prepared in the step (5) and a palladium-carbon catalyst in a mass ratio of 1: 0.15-0.2 in a solvent, wherein the volume mass ratio of the solvent to the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane is 25-30 mL:1g, heating to reflux, dropwise adding a 60-85% hydrazine hydrate solution into the system, wherein the volume mass ratio of the hydrazine hydrate solution to the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane is 2-5 mL:1g, dropwise adding the solution within 1-2 h, continuously heating and refluxing for 8-10 h, then adding tetrahydrofuran, filtering with a sand core funnel while hot to remove palladium carbon, and steaming to obtain a crude product, then recrystallizing and drying at the temperature of 80-100 ℃ in vacuum to obtain pure 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane, wherein the structural formula of the hexafluoropropane is as follows:
the solvent in the step (1) is methanol or ethanol, and the alkali is potassium hydroxide or sodium hydroxide; the solvent in the step (3) is a mixture of methanol, pyridine and water, the alkali is potassium hydroxide or sodium hydroxide, and the acid is concentrated hydrochloric acid or perchloric acid; the alkali in the step (4) is one of sodium carbonate, potassium carbonate and potassium iodide, and the solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide; the solvent in the step (5) is acetic acid, hydrochloric acid or perchloric acid, and the oxidant is 30% hydrogen peroxide; the solvent in the step (6) is methanol or ethanol.
The method has the advantages of easily obtained raw materials, controllable reaction temperature and higher yield and purity, and the prepared 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane can be used as a novel diamine monomer to react with some dianhydride to obtain a series of high-performance functional polymers such as novel fluorine-containing sulfonyl-containing polyamides, polyimides, polyamideimides and the like. Particularly, the novel polyimide obtained by the reaction of the diamine monomer and the dianhydride has excellent heat resistance, mechanical properties, and excellent optical properties and solubility due to the introduction of fluorine and sulfone groups.
Drawings
FIG. 1 shows FT-IR of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane obtained in the example of the present invention.
FIG. 2 shows 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl group prepared in the example of the present invention]Process for preparation of hexafluoropropane1H-NMR。
FIG. 3 shows 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl group prepared in the example of the present invention]Process for preparation of hexafluoropropane13C-NMR。
The monomer structure of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane was verified by the data shown on the spectra of fig. 1, 2 and 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example (b):
(1) synthesis of 2, 2-bis [4-N, N-dimethylthiooxyphenyl ] hexafluoropropane
NaOH (5.48 g, 0.095 mol) and absolute methanol (50 mL) were added into a three-necked flask (150 mL) equipped with a magnetic stirrer and a thermometer under nitrogen atmosphere, after the NaOH was completely dissolved, hexafluorobisphenol A (15.00 g, 0.045 mol) was added, and the mixture was stirred in an ice bath at 0 ℃ for 0.5 h, then N, N-dimethylthioacyl chloride (12.23 g, 0.095 mol) was added, and the mixture was stirred in the ice bath for 6 h. After the reaction is finished, suction filtration is carried out, and ice CH is used3OH/H2Washing with an O (V/V =1: 1) solution for 4-5 times, drying at 100 ℃ overnight, and using CHCl3/CH3Recrystallizing the OH (V/V =1: 3) solution to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethyl thio acyl hydroxyphenyl)]Hexafluoropropane, yield: 73 percent.
(2) Synthesis of 2, 2-bis [4-N, N-dimethylthioacyl mercapto phenyl ] hexafluoropropane
Adding 10 g of the monomer (1) into a 50 mL three-neck flask with mechanical stirring and a nitrogen inlet and outlet, gradually heating to 120 ℃ for reaction for 1 h, reacting at 220 ℃ for 2 h, reacting at 260 ℃ for 3 h, cooling to room temperature, adding a proper amount of dichloromethane to dissolve the product, performing rotary evaporation, performing vacuum drying at 40 ℃, and performing vacuum drying by using CH3OH/H2Recrystallizing O (V/V =3: 1) to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethyl thioacyl sulfydryl phenyl]Hexafluoropropane, yield 75%.
(3) Synthesis of 2, 2-bis [ 4-mercaptophenyl ] hexafluoropropane (3)
100 mL of methanol, 100 mL of pyridine, 20 mL of water and (27.50 g, 0.49 mol) of KOH were added to a 500 mL three-necked flask equipped with mechanical stirring and nitrogen blanketing, and after stirring until the KOH was completely dissolved, the intermediate 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl was added]Hexafluoropropane (25.0 g, 0.049 mol) was heated under reflux for 10 h under nitrogen, cooled to room temperature, diluted with 100 mL of water, acidified with 120 mL (12N) of concentrated HCl, filtered to give a white granular solid, and the filter cake was treated with CH3CH2OH:H2Recrystallizing the mixed solvent of O (V/V =3: 1) to obtain 2, 2-bis [ 4-mercaptophenyl-]Hexafluoropropane, yield 82%.
(4) Synthesis of 2, 2-bis [4- (4-nitrophenylthio) phenyl ] hexafluoropropane
2, 2-bis (4-mercaptophenyl) hexafluoropropane (10.0 g, 0.027 mol), 4-chloronitrobenzene (9.45 g, 0.060 mol), K, were each charged into a 250 mL three-necked flask equipped with mechanical stirring, thermometer, reflux condenser, and nitrogen inlet2CO3(8.96 g, 0.065 mol) and 100 mL of DMF, and the mixture is stirred under the protection of nitrogen and heated to 135 ℃ for reaction for 12 h. After the reaction is finished, decompressing and distilling part of DMF, pouring the concentrated reaction mixture into 500 mL ice water mixture after the temperature of the reaction mixture is reduced to room temperature to obtain yellow precipitate, filtering and collecting the product,washing with cold water repeatedly for several times, oven drying at 100 deg.C overnight, recrystallizing with ethanol-ethylene glycol monomethyl ether (V/V =5: 1) to obtain yellow needle crystal 2, 2-bis [4- (4-nitrophenylthio) phenyl]Hexafluoropropane, yield 72%.
(5) Synthesis of 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane
Adding (5 g, 0.0082 mol) intermediate (4) into a 150 mL single-neck flask which is provided with a reflux device and is magnetically stirred, then adding 50 mL glacial acetic acid and 5 mL of 30% hydrogen peroxide, setting the oil bath heating temperature to 120 ℃, heating to reflux, and reacting for 5 hours. After the reaction is finished, reduced pressure distillation is carried out, after the concentrated reaction mixture is cooled to room temperature, a reaction bottle is washed by a small amount of glacial acetic acid, the filtration and the washing are carried out, the reaction bottle is washed by distilled water, and after drying, 2-bis [4- (4-nitrobenzenesulfonyl) phenyl ] hexafluoropropane is obtained through recrystallization (DMF: absolute ethyl alcohol =4:10, V/V), and the yield is 80%.
(6) Synthesis of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane
Adding the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane (3 g, 0.0045 mol) prepared in the step (5), a 10% palladium-carbon catalyst (0.5 g) and 75 mL of ethanol into a 100 mL three-necked bottle provided with a mechanical stirrer, a condenser pipe and a nitrogen inlet, and heating to reflux; and then 7 mL of 85% hydrazine hydrate solution is dripped into a constant pressure dropping funnel for 1 h, after continuous reflux reaction is carried out for 9 h, the palladium-carbon is removed by filtration (sand core funnel) while the solution is hot, the solution is concentrated, precipitated in water and filtered to collect the product, and the product is separated and purified by silica gel column chromatography after being dried, thus obtaining the 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane. The yield is 75%; melting Point 240 ℃.
Claims (1)
1. A preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer is characterized by comprising the following steps:
(1) weighing alkali, N-dimethylthio acyl chloride and bisphenol A according to a molar ratio of 2-2.2: 1, and weighing an organic solvent according to a mass-volume ratio of the bisphenol A to the organic solvent of 1 g: 3-5 mL; under the protection of nitrogen, dissolving alkali by using an organic solvent, adding bisphenol A, and stirring 0 in an ice bath at 0 ℃.Adding N, N-dimethylthio acyl chloride for 5 hours, stirring and reacting for 4-6 hours at 0-5 ℃, and performing suction filtration after the reaction is finished, wherein the volume ratio of ice to CH is 1:13OH/H2Washing with O solution for 4-5 times, drying at 80-100 ℃ overnight, and recrystallizing to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethylthioacyl hydroxyphenyl]Hexafluoropropane;
(2) heating the 2, 2-bis [4-N, N-dimethylthioacyl hydroxyphenyl ] hexafluoropropane prepared in the step (1) to 100-120 ℃ for reaction for 1-2 h, reacting at 200-220 ℃ for 1-2 h, reacting at 240-280 ℃ for 2-3 h, cooling to room temperature, adding dichloromethane to dissolve the product, performing rotary evaporation, performing vacuum drying at 30-50 ℃, and then recrystallizing to obtain white solid powder, namely 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane;
(3) dissolving the 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane prepared in the step (2) and alkali in a molar ratio of 1: 1.0-1.2 in a solvent, wherein the volume mass ratio of the solvent to the 2, 2-bis [4-N, N-dimethylthioacyl mercaptophenyl ] hexafluoropropane is 4-10 mL:1g, heating and refluxing for 10-15 h under the protection of nitrogen, cooling, acidifying, performing suction filtration, and recrystallizing to obtain 2, 2-bis [ 4-mercaptophenyl ] hexafluoropropane;
(4) dissolving the 2, 2-bis (4-mercaptophenyl) hexafluoropropane and 4-chloronitrobenzene prepared in the step (3) in a solvent according to a molar ratio of 1: 2.0-2.2, simultaneously adding alkali, wherein the molar ratio of the alkali to the 2, 2-bis (4-mercaptophenyl) hexafluoropropane is 2-3: 1, the mass-volume ratio of the solvent to the 2, 2-bis (4-mercaptophenyl) hexafluoropropane is 1 g: 10-15 mL, heating to a stable reflux state, reacting for 10-15 h, cooling, filtering, and recrystallizing to obtain 2, 2-bis [4- (4-nitrobenzenethiophenyl) phenyl ] hexafluoropropane;
(5) oxidizing the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane prepared in the step (4) into 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane by using a solvent, wherein the molar volume ratio of the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane to the solvent is 1: 10-15 mL, heating to a reflux temperature, reacting for 3-8 h, cooling, filtering, and recrystallizing to obtain 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane;
(6) dissolving the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane prepared in the step (5) and a palladium-carbon catalyst in a mass ratio of 1: 0.15-0.2 in a solvent, wherein the volume mass ratio of the solvent to the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane is 25-30 mL:1g, heating to reflux, dropwise adding a 60-85% hydrazine hydrate solution into the system, wherein the volume mass ratio of the hydrazine hydrate solution to the 2, 2-bis [4- (4-nitrophenylsulfonyl) phenyl ] hexafluoropropane is 2-5 mL:1g, dropwise adding the solution within 1-2 h, continuously heating and refluxing for 8-10 h, then adding tetrahydrofuran, filtering with a sand core funnel while hot to remove palladium carbon, and steaming to obtain a crude product, then recrystallizing and drying at the temperature of 80-100 ℃ in vacuum to obtain pure 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane, wherein the structural formula of the hexafluoropropane is as follows:
the solvent in the step (1) is methanol or ethanol, and the alkali is potassium hydroxide or sodium hydroxide; the solvent in the step (3) is a mixture of methanol, pyridine and water, the alkali is potassium hydroxide or sodium hydroxide, and the acid is concentrated hydrochloric acid or perchloric acid; the alkali in the step (4) is one of sodium carbonate, potassium carbonate and potassium iodide, and the solvent is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide; the solvent in the step (5) is acetic acid, hydrochloric acid or perchloric acid, and the oxidant is 30% hydrogen peroxide; the solvent in the step (6) is methanol or ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010154323.1A CN111187187A (en) | 2020-03-07 | 2020-03-07 | Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010154323.1A CN111187187A (en) | 2020-03-07 | 2020-03-07 | Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111187187A true CN111187187A (en) | 2020-05-22 |
Family
ID=70704844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010154323.1A Pending CN111187187A (en) | 2020-03-07 | 2020-03-07 | Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111187187A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947480A (en) * | 1972-04-28 | 1976-03-30 | Uniroyal, Inc. | Dinitro- and diamino arylene disulfones |
| US4609712A (en) * | 1984-06-18 | 1986-09-02 | General Electric Company | Method for preparing monomeric and polymeric bis(dicarboxyphenyl) sulfone compounds |
| CN1061219A (en) * | 1990-11-05 | 1992-05-20 | 中国科学院长春应用化学研究所 | Synthesizing of diphenyl sulfone tetraformic acid and derivative thereof |
-
2020
- 2020-03-07 CN CN202010154323.1A patent/CN111187187A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947480A (en) * | 1972-04-28 | 1976-03-30 | Uniroyal, Inc. | Dinitro- and diamino arylene disulfones |
| US4609712A (en) * | 1984-06-18 | 1986-09-02 | General Electric Company | Method for preparing monomeric and polymeric bis(dicarboxyphenyl) sulfone compounds |
| CN1061219A (en) * | 1990-11-05 | 1992-05-20 | 中国科学院长春应用化学研究所 | Synthesizing of diphenyl sulfone tetraformic acid and derivative thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUI TONG 等: "Sulfonyl-Containing Polyimide Dielectrics with Advanced Heat Resistance and Dielectric Properties for High-Temperature Capacitor Applications", 《MACROMOL.MATER.ENG.》 * |
| 黄孝华: "新型功能性聚酰亚胺的合成与性能研究", 《上海交通大学博士学位论文》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI548634B (en) | Dianhydride and polyimide | |
| JP5443311B2 (en) | Polyimide precursor, polyimide resin and use thereof | |
| CN105693625B (en) | A kind of preparation method of the polyimide polymer with azapyrimidines construction unit | |
| JP4926550B2 (en) | Polyimide compound, process for producing the same, and optical material comprising the polyimide compound | |
| CN111961061B (en) | Dianhydride compound and preparation method and application thereof | |
| JP7096931B2 (en) | Fluorinated amide compounds, fluorinated nitrogen-containing heterocyclic compounds and fluorinated compounds | |
| CN110922594B (en) | High-light-transmittance soluble polyimide and preparation method of film thereof | |
| JP2537188B2 (en) | Polyimide | |
| CN111187187A (en) | Preparation method of 2, 2-bis [4- (4-aminophenylsulfonyl) phenyl ] hexafluoropropane diamine monomer | |
| Yin et al. | Synthesis and characterization of soluble polyimides based on trifluoromethylated aromatic dianhydride and substitutional diaminetriphenylmethanes | |
| CN114349726A (en) | 2,2 ' -difluoro-4, 4 ', 5,5 ' -biphenyl tetracarboxylic dianhydride monomer and preparation method and application thereof | |
| CN110156980B (en) | Colorless polyimide and preparation method and application thereof | |
| JPH05194338A (en) | 9,9-bis@(3754/24)4-aminophenyl)fluorenecarboxylic acid | |
| JP6266940B2 (en) | Arylene dioxy-bis (succinic anhydride) and method for producing the same | |
| WO2016095870A1 (en) | Bisphenol and diamine containing benzocyclobutene structural unit, and preparation and application thereof | |
| US5219978A (en) | Poly(arylene ether)from 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene | |
| CN115477629B (en) | Preparation method and application of tetrafluoroethyl bis (phthalic anhydride) derivative | |
| CN115557848B (en) | Diamine monomer, low CTE, high permeability polyimide and preparation method thereof | |
| CN118063334A (en) | Vanillin-derived diamine monomer and polyimide containing trifluoro vinyl ether structure, and preparation methods and applications thereof | |
| JP2002256072A (en) | Synthesis of polyetherketone (ppek) having phthalazine structure | |
| CN115433359B (en) | Soybean element bio-based polyimide and preparation and application thereof | |
| CN114891210B (en) | Polyimide, polyimide film and preparation method thereof | |
| TWI790043B (en) | Preparation method of dinitro compound, diamine and preparation method thereof, and polyimide | |
| KR101685673B1 (en) | Poly(biphenylene oxide)s Substituted with Two Trifluoromethyl Groups and Method for Producing Thereof | |
| JPS6315827A (en) | Diacetylene group-containing polyamic acid and polyimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200522 |