CN111100016A - Preparation method of aliphatic ring bridged aromatic diamine monomer - Google Patents
Preparation method of aliphatic ring bridged aromatic diamine monomer Download PDFInfo
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- CN111100016A CN111100016A CN201911405912.6A CN201911405912A CN111100016A CN 111100016 A CN111100016 A CN 111100016A CN 201911405912 A CN201911405912 A CN 201911405912A CN 111100016 A CN111100016 A CN 111100016A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C209/78—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 from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Abstract
The invention relates to a preparation method of an aliphatic ring bridged aromatic diamine monomer, belonging to the technical field of preparation of diamine monomers for polyimide. The invention relates to a method for preparing aliphatic ring bridged aromatic diamine monomer, which takes naphthenic ketone and amine as raw materials, takes methylbenzene as entrainer and uses the materials in perfluorosulfonic acid resin/SiO2Nucleophilic reaction is carried out under the action of a solid acid catalyst, and then post-treatment is carried out to obtain the aliphatic ring bridged aromatic diamine monomer. The invention not only reduces the reaction temperature, shortens the reaction time, improves the reaction yield, but also reduces the toxicity of post-treatment, reduces the production cost and has wide application range.
Description
Technical Field
The invention relates to a preparation method of an aliphatic ring bridged aromatic diamine monomer, belonging to the technical field of preparation of diamine monomers for polyimide.
Background
Polyimide (PI) is a well-known polymeric material with excellent thermal stability, good dielectric properties, chemical resistance and dimensional stability. However, most of the conventional aromatic polyimide films are generally light yellow to dark brown, have low visible light transmittance (wavelength of 400-700 nm), have a transmittance of less than 40% at 500nm, and are 100% absorbed at around 400nm, which severely limits the applications in the optical or optical-electrical fields such as flexible solar radiation protective films, liquid crystal display orientation films, optical half-wave conductor materials and the like. The principle behind increasing PI transparency is to avoid or reduce conjugated units and to reduce intramolecular or intermolecular charge transfer. The alicyclic structure is introduced into the PI molecule, so that the formation of charge transfer complexes in and among the PI molecules can be effectively inhibited, and the absorption of the PI in an ultraviolet-visible light region can be obviously weakened.
At present, the method for synthesizing alicyclic diamine monomer represented by 1,1-bis (4-aminophenyl) cyclohexane (BACH) mainly comprises the nucleophilic reaction of amine and cycloalkyl ketone under the catalysis of hydrochloric acid, or the nucleophilic reaction of hydrochloride of amine and cycloalkyl ketone directly, but the existing synthesis method generally has the problems of high reaction temperature, long time, low yield and the like, benzene with high toxicity is commonly used as a recrystallization solvent in the post-treatment, and activated carbon is also needed for color removal in some cases, thereby further increasing the cost.
The synthetic literature (Macromolecules,1997,30, 5606-.
The literature (Journal of Organic Chemistry,2013,78,72-59-7263, Guanidine-guindinium Cooperation in Bifunctional aromatic phosphorus basic dimethyl methane Spacers; gemDialkyl Effect on Catalytic Effect) uses 35% hydrochloric acid as catalyst, the BACH yield is 60%, the reaction temperature is up to 150 ℃, and the reaction time is up to 48 h.
The literature (Spectroscopy Letters,40:1,97-112,2007, Microwave Irradded and chemical Syntheses of symmetry Double Schiff Bases of 1,1' -Bis (4-aminophe-nyl) cyclohexamine and the same physical catalysis) uses amine salts as starting materials, no catalyst, relatively short reaction times of 11h, reaction temperatures of 120 and 150 ℃, BACH yields of only 32%, and benzene-n-hexane as a recrystallization solvent for the work-up.
The literature (Journal of Polymer Science: Part A: Polymer Chemistry, Vol.37, 3449-3454 (1999), Synthesis and characterization of solvent polymers from 2,2-Bis (4-aminophenyl) cyclic alkan Derivatives) does not use catalysts, the reaction temperature of 2,2-Bis (4-aminophenyl) norbonone synthesis is up to 140-.
Based on the prior art, the method optimizes the process conditions, reduces the reaction temperature, shortens the reaction time, improves the reaction efficiency and yield, and has industrial production value.
Disclosure of Invention
The invention aims to provide a preparation method of an aliphatic ring bridged aromatic diamine monomer, which not only reduces the reaction temperature, shortens the reaction time, improves the reaction yield, but also reduces the toxicity of post-treatment, reduces the production cost and has wide application range.
The preparation method of the aliphatic ring bridged aromatic diamine monomer takes naphthenic-base ketone and amine as raw materials, takes methylbenzene as an entrainer and adopts the method that the raw materials are added into perfluorinated sulfonic acid resin/SiO2Nucleophilic reaction is carried out under the action of a solid acid catalyst, and then post-treatment is carried out to obtain the aliphatic ring bridged aromatic diamine monomer.
The cycloalkyl ketone is preferably cyclohexanone, 4-methylcyclohexanone, 3, 5-trimethylcyclohexanone, 2-adamantanone or 2-norborneone.
The amine is preferably aniline, 2, 6-dimethylaniline or 2, 6-difluoroaniline.
The molar ratio of the naphthenic ketone to the amine is 1: 3-5.
The molar ratio of the naphthenic ketone to the toluene is 1.7-4.3: 1.
The reaction temperature is 110-115 ℃.
The reaction time is 6.5-9.5 h.
The post-treatment comprises pH adjustment, liquid separation, reduced pressure distillation, pulping, filtration and drying.
The pulping solvent is a petroleum ether-ethanol system.
The volume ratio of the petroleum ether to the ethanol is 8:1-10: 1.
The perfluorinated sulfonic acid resin/SiO2The solid acid catalyst is reused for 3-5 times.
The perfluorinated sulfonic acid resin/SiO2The solid acid catalyst is prepared by referring to the method disclosed in patent CN105665018A of the same company, and the specific preparation method is as follows:
adding the perfluorinated sulfonic acid resin with the exchange capacity of 1.1 into an ethanol-water solution, mechanically stirring for 8 hours at 250 ℃ under a high-pressure reflux device, and evaporating and concentrating to obtain a perfluorinated sulfonic acid resin solution with the solid content of 5%. Adding 13.84g of deionized water into 40g of n-silane ethyl ester, then adding 10ml of 0.04mol/L HCl solution under stirring, continuing to add the hydrolyzed n-ethyl orthosilicate solution into a mixed solution of 38.44g of perfluorosulfonic acid resin and 38.44g of 0.05mol/L NaOH under stirring after stirring until the solution is clear, allowing the solution to gel quickly, then covering the gel on aluminum foil paper, drying for 2 days at 75 ℃, then removing the aluminum foil paper, drying for 1 day in a constant-temperature drying oven at 95 ℃ to obtain solid particles, and finally drying the solid particles for 1.5 days at 140 ℃ in a vacuum drying oven to obtain completely dried solid particles. Then crushing the solid particles, soaking for 5 times with 3.5mol/L HCl solution for 5min each time, then washing with pure water for 3min each time, drying, and then calcining the dried solid particles at high temperature of 320 ℃ to obtain the perfluorosulfonic acid resin/SiO2A solid acid catalyst.
The reaction equation involved in the invention is as follows
The invention has the following beneficial effects:
(1) the invention has stronger universality, and relates to a plurality of selection types of raw materials of amine and ketone;
(2) the invention uses self-made perfluorinated sulfonic acid resin/SiO2The superstrong solid acid is used as a catalyst, and the toluene is added as an entrainer, so that water generated in the reaction can be removed, the forward progress of the reaction is promoted, the reaction temperature of 120-160 ℃ is reduced to 115-110 ℃, and the production safety is improved; the reaction time is shortened from tens to twenty hours to 6.5-9.5 hours; in addition, the yield is improved from 32-79.4% to 63.2-89.8%;
(3) the invention improves the post-treatment mode, replaces the mode of recrystallization by taking benzene as a solvent, reduces the toxicity and obtains a product with the purity of more than 99 percent and excellent color; the use of activated carbon for color removal is avoided, and the cost is reduced;
(4) in the invention, the self-made solid acid catalyst is used, so that the corrosivity to the reactor is reduced, the reusability is good, and the reduction of the catalytic efficiency is not obvious after the catalyst is reused for 3-5 times.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The perfluorinated sulfonic acid resin/SiO2The solid acid catalyst is prepared by the method disclosed in patent CN105665018A of the company, and the specific preparation method is as follows:
adding the perfluorinated sulfonic acid resin with the exchange capacity of 1.1 into an ethanol-water solution, mechanically stirring for 8 hours at 250 ℃ under a high-pressure reflux device, and evaporating and concentrating to obtain a perfluorinated sulfonic acid resin solution with the solid content of 5%. Adding 13.84g of deionized water into 40g of n-silane ethyl ester, then adding 10ml of 0.04mol/L HCl solution under stirring, continuing to add the hydrolyzed n-ethyl orthosilicate solution into a mixed solution of 38.44g of perfluorosulfonic acid resin and 38.44g of 0.05mol/L NaOH under stirring after stirring until the solution is clear, allowing the solution to gel quickly, then covering the gel on aluminum foil paper, drying for 2 days at 75 ℃, then removing the aluminum foil paper, drying for 1 day in a constant-temperature drying oven at 95 ℃ to obtain solid particles, and finally drying the solid particles for 1.5 days at 140 ℃ in a vacuum drying oven to obtain completely dried solid particles. Then crushing the solid particles, soaking with 3.5mol/L HCl solution for 5 times, each for 5min, then washing with pure water for 3min each,drying, and calcining the dried solid particles at the high temperature of 320 ℃ to obtain the perfluorinated sulfonic acid resin/SiO2A solid acid catalyst.
Example 1
To a three-necked flask equipped with an azeotropic vaporizer was added 8g of the solid acid catalyst prepared above, and then 25g (0.255mol) of cyclohexanone, 13.82g (0.15mol) of toluene and 71.2g (0.764mol) of aniline were added to react at 115 ℃ for 8 hours, and after cooling to room temperature, the catalyst was filtered off, washed with ethanol, and dried at 50 ℃ for 3 hours for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml solution of V (petroleum ether) and V (ethanol) 9:1 at 0 deg.C, precipitating white solid product BACH, filtering, drying, and obtaining product yield of 67% and purity of 99%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 82.2%, 81.8% and 81.3% in sequence.
Example 2
To a three-necked flask equipped with an azeotropic condenser, 8g of the solid acid catalyst prepared above was charged, and then 25g (0.255mol) of cyclohexanone, 13.82g (0.15mol) of toluene and 118.7g (1.27mol) of aniline were added to react at 115 ℃ for 8 hours, and after cooling to room temperature, the catalyst was filtered off, washed with ethanol, and dried at 50 ℃ for 3 hours for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with yield of 89.2% and purity of 99.3%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 89.2%, 88.5% and 87.8% in sequence.
Example 3
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 13.82g (0.15mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 115 ℃ for 8h, after cooling to room temperature, the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with yield of 89.8% and purity of 99.5%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 89.8%, 87.6% and 88.1% in sequence.
Example 4
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 115 ℃ for 8h, after cooling to room temperature, the catalyst was filtered off, washed with ethanol, and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with the yield of 88.9% and the purity of 99.2%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 88.9 percent, 89.1 percent and 88.1 percent in sequence.
Example 5
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 5.6g (0.06mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 115 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with yield of 75.2% and purity of 99%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 75.2%, 74.6% and 73.9% in sequence.
Example 6
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 115 ℃ for 8h, after cooling to room temperature, the catalyst was filtered off, washed with ethanol, and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 by using a NaOH solution, separating the solution, distilling off excessive aniline (the aniline can be repeatedly used) by using an organic phase under reduced pressure, adding 100ml of a solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out a white solid product BACH, filtering, drying, and obtaining the product with the yield of 89.4% and the purity of 99.2%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for five times, and the yields are 89.4%, 88.2%, 87.5%, 86.8% and 85.9% in sequence.
Example 7
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 9.5h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with the yield of 88.4% and the purity of 99.3%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 88.4%, 87.5% and 86.2% in sequence.
Example 8
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 6.5h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with the yield of 70.5% and the purity of 99.3%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 72.1%, 71.4% and 71.1% in sequence.
Example 9
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 8:1, pulping at 0 ℃, separating white solid product BACH, filtering, drying, obtaining yield of 82.8% and purity of 99.5%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 82.8%, 82.5% and 80.9% in sequence.
Example 10
8g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml solution of V (petroleum ether) and V (ethanol) 10:1, pulping at 0 deg.C, precipitating white solid product BACH, filtering, drying, and obtaining yield of 89% and purity of 85%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 89%, 88.5% and 88.3% in sequence.
Example 11
6g of the solid acid catalyst prepared above was added to a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with yield of 71.5% and purity of 99%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yield is 71.5 percent, 70.7 percent and 69 percent in sequence.
Example 12
10g of the solid acid catalyst prepared above was charged into a three-necked flask equipped with an entrainer, then 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solid product BACH, filtering, drying, and obtaining the product with the yield of 88.7% and the purity of 99.4%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 88.7%, 88.2% and 87.6% in sequence.
Example 13
Adding 8g of the solid acid catalyst prepared in the previous step into a three-neck flask provided with an azeotrope reactor, adding 28g (0.255mol) of 2-norborneone, 9.2g (0.1mol) of toluene and 94.9g (1.02mol) of aniline, reacting at 110 ℃ for 8h, cooling to room temperature, filtering the catalyst, washing with ethanol, and drying at 50 ℃ for 3h for repeated use. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating the solution, distilling off excessive aniline (the aniline can be reused) by organic phase under reduced pressure, adding 100ml of a solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solids, namely the target product, filtering, drying, and obtaining the product with the yield of 74.2% and the purity of 99.1%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yield is 74.2 percent, 72.9 percent and 71.5 percent in sequence.
Example 14
8g of the solid acid catalyst prepared above was charged into a three-necked flask equipped with an entrainer, then 38g (0.255mol) of 2-adamantanone, 9.2g (0.1mol) of toluene and 123.6g (1.02mol) of 2, 6-dimethylaniline were added to react at 110 ℃ for 8h, after cooling to room temperature, the catalyst was filtered off, washed with ethanol and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating white solid, namely the target product, filtering, drying, and obtaining the product with the yield of 68.4% and the purity of 99%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yields are 68.4 percent, 67.9 percent and 66.3 percent in sequence
Example 15
To a three-necked flask equipped with an entrainer was added 8g of the solid acid catalyst prepared above, followed by addition of 28.6g (0.255mol) of 4-methylcyclohexanone, 9.2g (0.1mol) of toluene and 131.7g (1.02mol) of 2, 6-difluoroaniline at 110 ℃ for 8h, cooling to room temperature and then filtering off the catalyst, washing with ethanol, and drying at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating the solution, distilling off excessive aniline (the aniline can be reused) by organic phase under reduced pressure, adding 100ml of a solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solids, namely the target product, filtering, drying, wherein the product yield is 63.2%, and the purity is 99.3%. The yield of the reaction is not obviously reduced after the catalyst is repeatedly used for three times, and the yield is 63.2 percent, 64.1 percent and 62.4 percent in sequence.
Comparative example 1
29.79g (0.23mol) aniline hydrochloride and 9.8g (0.1mol) cyclohexanone react at 120 ℃ for 2h, then react at 145 +/-5 ℃ for 9h, the temperature is reduced to 120 ℃, 50ml boiling water is added, the reaction liquid is dark red, active carbon is continuously added into the solution to reflux for 20min, then the active carbon is filtered out, the reaction liquid becomes clear, 10% sodium hydroxide solution is added to convert amine salt into amine, the solid product is filtered out, the solid product is washed by distilled water and dried at 50 ℃, then the product is recrystallized in a benzene-n-hexane system to obtain a bright brown needle-shaped crystal product, and the product yield is 32%.
Comparative example 2
Adding excessive aniline 10ml (110mmol) into cyclohexanone 3g (30.6mmol) and 11ml 35% hydrochloric acid solution, reacting at 150 deg.C for 48h, cooling, adjusting pH to 13 with NaOH solution, separating, distilling off excessive aniline by organic phase vacuum distillation, and purifying the rest product by column chromatography (SiO)2N-hexane: ethyl acetate 10:1-3:1) to give the product as a pale yellow solid, 4.91g (18.4mmol) with a product yield of 60%.
Comparative example 3
8g of the solid acid catalyst prepared above was added to a three-necked flask, then 25g (0.255mol) of cyclohexanone and 94.9g (1.02mol) of aniline were added to react at 110 ℃ for 8h, after cooling to room temperature the catalyst was filtered off, washed with ethanol, and dried at 50 ℃ for 3h for reuse. Adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline (aniline can be reused) by organic phase under reduced pressure, adding 100ml of solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating white solid, namely the target product, filtering, drying, and obtaining the product with the yield of 64.9% and the purity of 99.2%.
Comparative example 4
Adding 25g (0.255mol) of cyclohexanone, 9.2g (0.1mol) of toluene and 132.2g (1.02mol) of aniline hydrochloride into a three-neck flask provided with an entrainer to react for 8h at 110 ℃, cooling to room temperature, adjusting the pH of the reaction solution to 10 with NaOH solution, separating, distilling off excessive aniline by taking organic phase under reduced pressure (the aniline can be reused), adding 100ml of a solution of V (petroleum ether) and V (ethanol) 9:1, pulping at 0 ℃, separating out white solids, namely the target product, filtering and drying, wherein the yield of the product is 55.3%, and the purity is 99%.
Claims (10)
1. A preparation method of an aliphatic ring bridged aromatic diamine monomer is characterized by comprising the following steps: using cycloalkyl ketone and amine as raw materials, toluene as an entrainer and in perfluorosulfonic acid resin/SiO2Reacting under the action of a solid acid catalyst, and then carrying out post-treatment to obtain the aliphatic ring bridged aromatic diamine monomer.
2. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the cycloalkyl ketone is cyclohexanone, 4-methylcyclohexanone, 3, 5-trimethylcyclohexanone, 2-adamantanone or 2-norborneone.
3. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the amine is aniline, 2, 6-dimethylaniline or 2, 6-difluoroaniline.
4. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the molar ratio of the cycloalkyl ketone to the amine is 1: 3-5.
5. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the molar ratio of the cycloalkyl ketone to the toluene is 1.7-4.3: 1.
6. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the reaction temperature is 110-115 ℃, and the reaction time is 6.5-9.5 h.
7. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: the post-treatment comprises pH adjustment, liquid separation, reduced pressure distillation, pulping, filtration and drying.
8. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 7, wherein: the pulping solvent is a petroleum ether-ethanol system.
9. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 8, wherein: the volume ratio of the petroleum ether to the ethanol is 8:1-10: 1.
10. The method for preparing an aliphatic ring-bridged aromatic diamine monomer according to claim 1, comprising the steps of: perfluorosulfonic acid resin/SiO2The solid acid catalyst is reused for 3-5 times.
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