CN114349649A - Two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structure at the same time and preparation method thereof - Google Patents

Abstract

The invention discloses two aromatic diamine monomers containing both methoxyfluorene and methyl structure, namely 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl]Fluorene and 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl]Fluorene, which has the chemical structural formula:

and

the melting points are 259-260 ℃ and 262-263 ℃ respectively. Also discloses a preparation method of two aromatic diamine monomers containing both methoxyfluorene and methyl structure. The invention has simple synthesis process route, high yield and easy purification, has a plurality of side groups and large free volume, and can be further condensed with aromatic dianhydride and aromatic diacid to prepare high-performance polyimide and polyaramide membrane materials.

Description

Two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structure at the same time and preparation method thereof

technical field

The invention belongs to the field of aromatic diamine monomer compounds and preparations thereof, in particular to two aromatic diamine monomers containing methoxyfluorene and methyl structures and a preparation method thereof.

Background technique

Polyimide and polyaramid are two important aromatic special polymer materials, which can be widely used as membrane materials in gas separation, ultrafiltration, reverse osmosis and other membrane separation fields. Polyimides and polyaramides are mainly prepared by polycondensation of aromatic diamines, aromatic dianhydrides and aromatic diacid monomers. The structure of the monomers directly has a decisive influence on the properties of the prepared polymers. Fluorene-containing aromatic diamine monomers are considered to be an important class of high-performance aromatic diamine monomers due to their rigid non-coplanar structure. The introduction of fluorene-based non-coplanar structure can effectively improve the dissolution and synthesis of the prepared aromatic polymers. Membrane properties and membrane separation performance. However, the varieties of fluorene-containing aromatic diamine monomers that have been commercialized at present are very limited, mainly 9,9-bis(4-aminophenyl)fluorene and its derivatives. Therefore, it is of great academic and practical value to design and develop novel aromatic diamine monomers containing fluorene structure and perform molecular modification in order to further improve the properties of the prepared aromatic polymers.

Based on this, the patent of the present invention intends to use bisphenol fluorene derivatives as starting materials to design and prepare two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structures through a two-step conventional organic reaction. The structure of the aromatic diamine monomer further introduces multiple methoxy groups and methyl groups to increase the steric free volume of the diamine structure, which is expected to further improve the properties of the corresponding polymer membrane materials.

SUMMARY OF THE INVENTION

The purpose of the present invention is to expand the varieties of fluorene-containing aromatic diamine monomers to meet social needs, and to provide two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structures at the same time and a preparation method thereof.

The purpose of the patent of the present invention is to design and prepare two kinds of aromatic diamine monomers containing both methoxyfluorene and methyl structures through a two-step conventional organic reaction, and further introduce a plurality of methoxyl groups into the structure of the fluorene-containing aromatic diamine monomer. group and methyl group to increase the steric free volume of the diamine structure, which is expected to further improve the properties of the corresponding polymer membrane materials.

In order to achieve the above purpose, the present invention provides two aromatic diamine monomers containing both methoxyfluorene and methyl structures through a simple synthetic route, namely 9,9-bis[3,5-dimethoxy- 4-(2-Methyl-4-aminophenoxy)phenyl]fluorene and 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-aminophenoxy) base) phenyl] fluorene, and its chemical structural formula is respectively:

The monomer is a white needle-like crystal powder with melting points of 259-260 and 262-263°C, respectively.

The invention also provides a preparation method of the above two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structures at the same time, the specific steps are:

(1) In a three-necked flask equipped with mechanical stirring and nitrogen protection, dissolve the bisphenol compound containing methoxyfluorene structure and two different fluorine-containing nitrobenzenes in a molar ratio of 1:2.0-2.3 in an appropriate amount of organic In the solvent, under the action of a certain amount of basic catalyst, the reaction is stirred at 100 to 150 ° C for 6 to 12 hours, and the reaction is terminated. The reactants are poured into water for sedimentation. A dinitro compound containing both methoxyfluorene and methyl structures: 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-nitrophenoxy)phenyl ] fluorene and 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-nitrophenoxy)phenyl]fluorene.

The bisphenol compound containing methoxyfluorene structure is 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene; the fluorine-containing nitrobenzene is 2-fluoro-5-nitrotoluene and 5-Fluoro-2-nitrotoluene from which the intermediate dinitro compound 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-nitrophenoxy)benzene was prepared The fluorine-containing nitrobenzene used in the preparation of fluorene is 2-fluoro-5-nitrotoluene, and the intermediate dinitro compound 9,9-bis[3,5-dimethoxy-4-(3- The fluorine-containing nitrobenzene used in methyl-4-nitrophenoxy)phenyl]fluorene is 5-fluoro-2-nitrotoluene.

The above-mentioned organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, and its quality is the bisphenol compound 9,9-bis(3,5-dimethoxy) 2-3 times the total mass of fluorene and 2-fluoro-5-nitrotoluene (or 5-fluoro-2-nitrotoluene); the basic catalyst is potassium carbonate or sodium carbonate, and its mole The number is 2.0 to 3.0 times the mole number of the bisphenol compound 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene.

(2) adding the dinitro compound obtained in the step (1) and a certain amount of organic solvent into the three-necked flask, further adding a certain amount of reducing agent and catalyst, stirring and heating to reflux under reflux for 4～20h to finish the reaction, heat After filtration and cooling, white needle-like crystals were obtained, which was further filtered and dried to obtain two diamine compounds containing both methoxyfluorene and methyl structures: 9,9-bis[3,5-dimethoxy- 4-(2-Methyl-4-aminophenoxy)phenyl]fluorene and 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-aminophenoxy) base) phenyl] fluorene.

Wherein the organic solvent is a mixed solvent of 1:1.0～3.0 ethanol and ethylene glycol methyl ether, and its mass is 3～6 times of the mass of the dinitro compound; the catalyst is palladium carbon whose mass fraction is 5% or 10% of palladium, The catalyst dosage is 2% to 4% of the mass of the dinitro compound; the reducing agent is a hydrazine hydrate solution with a solute mass fraction of 80%, and the dosage is 4 to 12 times the mole number of the dinitro compound.

The concrete synthetic routes of two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structure provided by the patent of the present invention are as follows:

The beneficial effects of the present invention are:

(1) Two kinds of aromatic diamine monomers containing methoxyfluorene and methyl structure at the same time provided by the present invention and preparation methods thereof, the synthesis method is simple, the product separation is convenient, the yield is high, the stability is good, and it is easy to industrialize scale up production;

(2) The aromatic diamine monomer provided by the present invention has a large free volume, and can be further polycondensed with aromatic dianhydride and aromatic diacid to prepare high-performance polyimide and polyaramide film materials.

Description of drawings

Fig. 1 is Example 1, the intermediate dinitro compound 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-nitrophenoxy)phenyl]fluorene ¹ H NMR spectrum.

Figure 2 is the ¹ H NMR of the aromatic diamine 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-aminophenoxy)phenyl]fluorene in Example 1 Atlas.

Fig. 3 is Example 3, the intermediate dinitro compound 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-nitrophenoxy)phenyl]fluorene ¹ H NMR spectrum.

Figure 4 is the ¹ H NMR of the aromatic diamine 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-aminophenoxy)phenyl]fluorene in Example 3 Atlas.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

The preparation method of two kinds of aromatic diamine monomers containing methoxy fluorene and methyl structure at the same time, the concrete steps are:

(1) In a 500ml dry three-necked flask equipped with nitrogen protection, mechanical stirring and a condenser, add 47.05g (0.1mol) of 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene respectively , 31.02g (0.2mol) containing 2-fluoro-5-nitrotoluene, 27.64g (0.2mol) potassium carbonate and 170ml N,N-dimethylformamide, after stirring and reacting at 100 ° C for 12h, poured into ice Stir and settle in a water bath, a large amount of solids are precipitated, and the crude product is further recrystallized with N,N-dimethylformamide to obtain a white crystalline powder, which is the intermediate dinitro compound 9,9-bis[3,5 -Dimethoxy-4-(2-methyl-4-nitrophenoxy)phenyl]fluorene in 85% yield.

¹ H NMR (CDCl ₃ , 400MHz) of the above-mentioned dinitro compound 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-nitrophenoxy)phenyl]fluorene As shown in Figure 1.

(2) In a 500ml three-necked flask, add 37.04g (0.05mol) of the dinitro compound 9,9-bis[3,5-dimethoxy-4-(2-methyl) obtained in step (1) respectively yl-4-nitrophenoxy)phenyl]fluorene, 0.75g 5% (palladium mass fraction, the same below) palladium-carbon catalyst, 130ml ethanol/ethylene glycol methyl ether mixed solvent (volume ratio is 1:3.0), Under stirring, be warming up to the reflux state; use the constant pressure dropping funnel to add dropwise the hydrazine hydrate solution of 14ml 80% (solute mass fraction, the same below) in 30min, continue the reflux reaction for 4 hours, remove the palladium carbon by hot filtration, concentrate, Add water to precipitate, and the crude product is recrystallized from ethylene glycol methyl ether to obtain 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-aminophenoxy)phenyl] Fluorene in 84% yield.

The ¹ HNMR (CDCl ₃ , 400MHz) of the above-mentioned diamine monomer 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-aminophenoxy)phenyl]fluorene is as follows: Figure 2 shows.

Example 2

The preparation method of two kinds of aromatic diamine monomers containing methoxy fluorene and methyl structure at the same time, the concrete steps are:

(1) In a 500ml dry three-necked flask equipped with nitrogen protection, mechanical stirring and a condenser, add 47.05g (0.1mol) of 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene respectively , 35.65 g (0.23 mol) of 2-fluoro-5-nitrotoluene, 41.46 g (0.3 mol) of potassium carbonate and 245 ml of N-methylpyrrolidone were stirred and reacted at 150 ° C for 6 h, poured into an ice-water bath, stirred and settled, A large amount of solid was precipitated, which was filtered and dried, and the crude product was further recrystallized with N,N-dimethylformamide to obtain a white crystalline powder, which was the intermediate dinitro compound 9,9-bis[3,5-dimethoxyl -4-(2-Methyl-4-nitrophenoxy)phenyl]fluorene in 86% yield.

(2) In a 500ml three-necked flask, add 37.04g (0.05mol) of the dinitro compound 9,9-bis[3,5-dimethoxy-4-(2-methyl) obtained in step (1) respectively yl-4-nitrophenoxy)phenyl]fluorene, 1.2g 10% (palladium mass fraction, the same below) palladium-carbon catalyst, 180ml ethanol/ethylene glycol methyl ether mixed solvent (volume ratio is 1:2.0), Under stirring, be warming up to the reflux state; use the constant pressure dropping funnel to add dropwise the hydrazine hydrate solution of 30ml 80% (solute mass fraction, the same below) in 30min, continue the reflux reaction for 12 hours, remove the palladium carbon by hot filtration, concentrate, Add water to precipitate, and the crude product is recrystallized from ethylene glycol methyl ether to obtain 9,9-bis[3,5-dimethoxy-4-(2-methyl-4-aminophenoxy)phenyl] Fluorene in 83% yield.

Example 3

The preparation method of two kinds of aromatic diamine monomers containing methoxy fluorene and methyl structure at the same time, the concrete steps are:

(1) In a 500ml dry three-necked flask equipped with nitrogen protection, mechanical stirring and a condenser, add 47.05g (0.1mol) of 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene respectively , 31.02g (0.2mol) of 5-fluoro-2-nitrotoluene, 41.46g (0.3mol) of potassium carbonate and 180ml of N,N-dimethylacetamide, stirred at 150°C for 12h, poured into ice Stir and settle in a water bath, a large amount of solids are precipitated, and the crude product is further recrystallized with N,N-dimethylformamide to obtain a white crystalline powder, which is the intermediate dinitro compound 9,9-bis[3,5 -Dimethoxy-4-(3-methyl-4-nitrophenoxy)phenyl]fluorene in 86% yield.

¹ H NMR (CDCl ₃ , 400MHz) of the above-mentioned dinitro compound 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-nitrophenoxy)phenyl]fluorene As shown in Figure 3.

(2) In a 500ml three-necked flask, add 37.04g (0.05mol) of the dinitro compound 9,9-bis[3,5-dimethoxy-4-(3-methyl) obtained in step (1) respectively yl-4-nitrophenoxy)phenyl]fluorene, 0.14g 5% (palladium mass fraction, the same below) palladium-carbon catalyst, 130ml ethanol/ethylene glycol methyl ether mixed solvent (volume ratio is 1:2.0), Under stirring, be warming up to under the reflux state; Use the constant pressure dropping funnel to add dropwise the hydrazine hydrate solution of 14ml 80% (solute mass fraction, the same below) in 30min again, continue the reflux reaction for 10 hours, remove the palladium carbon by hot filtration, concentrate, Add water to precipitate, and the crude product is recrystallized from ethylene glycol methyl ether to obtain 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-aminophenoxy)phenyl] Fluorene in 84% yield.

The ¹ H NMR (DMSO-d ₆ , 400MHz) of the above 9,9-bis[3,5-dimethoxy-4-(3-methyl-4-aminophenoxy)phenyl]fluorene is as attached shown in Figure 4.

Example 4

The preparation method of two kinds of aromatic diamine monomers containing methoxy fluorene and methyl structure at the same time, the concrete steps are:

(1) In a 500ml dry three-necked flask equipped with nitrogen protection, mechanical stirring and a condenser, add 47.05g (0.1mol) of 9,9-bis(3,5-dimethoxy-4-hydroxy)fluorene respectively , 35.65g (0.23mol) containing 5-fluoro-2-nitrotoluene, 27.64g (0.2mol) potassium carbonate and 180ml N-methylpyrrolidone, after stirring and reacting at 150 ° C for 6h, poured into an ice-water bath, stirring and settling , a large amount of solid was precipitated, which was filtered and dried, and the crude product was further recrystallized with N,N-dimethylformamide to obtain a white crystalline powder, which was the intermediate dinitro compound 9,9-bis[3,5-dimethoxy yl-4-(3-methyl-4-nitrophenoxy)phenyl]fluorene in 84% yield.

(2) in the three-necked flask of 500ml, respectively add 37.04g (0.05mol) dinitro compound obtained in step (1), 0.8g 10% (palladium mass fraction, the same below) palladium-carbon catalyst, 200ml ethanol/ethyl alcohol Glycol methyl ether mixed solvent (volume ratio is 1:2.0), heat up to reflux state with stirring; use constant pressure dropping funnel to add 20ml 80% (solute mass fraction, the same below) hydrazine hydrate solution dropwise within 30min , continue the reflux reaction for 4 hours, remove the palladium carbon by hot filtration, concentrate, add water for precipitation, and recrystallize the crude product from ethylene glycol methyl ether to obtain 9,9-bis[3,5-dimethoxy-4-(3 -Methyl-4-aminophenoxy)phenyl]fluorene in 83% yield.

Claims (8)

1. Two aromatic diamine monomers containing both methoxyfluorene and methyl structure are characterized in that: the aromatic diamine monomer is 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl ] fluorene and 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl ] fluorene, and the chemical structural formulas of the aromatic diamine monomer are respectively as follows:

the melting points are 259-260 ℃ and 262-263 ℃ respectively.

2. The method for preparing two aromatic diamine monomers containing both methoxyfluorene and methyl structure as claimed in claim 1, wherein: the method comprises the following specific steps:

(1) dissolving a bisphenol compound containing a methoxyfluorene structure and two different fluoronitrobenzene in a proper amount of organic solvent according to a molar ratio of 1: 2.0-2.3 in a three-neck flask with mechanical stirring and nitrogen protection, stirring and reacting for 6-12 h under the action of a certain amount of alkaline catalyst at 100-150 ℃, then finishing the reaction, pouring the reactant into water for settling, performing suction filtration and drying on a crude product, and further recrystallizing to respectively obtain two dinitro compounds containing both methoxyfluorene and methyl structure: 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene and 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl ] fluorene;

(2) adding the dinitro compound obtained in the step (1) and a certain amount of organic solvent into a three-neck flask, further adding a certain amount of reducing agent and catalyst, stirring and heating until the reaction is finished after 4-20 h under reflux, thermally filtering, cooling, separating out white needle-shaped crystals, further filtering and drying to respectively obtain two diamino compounds simultaneously containing methoxyfluorene and methyl structure: 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl ] fluorene and 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl ] fluorene.

3. The method of claim 2, wherein: the bisphenol compound containing the methoxyfluorene structure in the step (1) is 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene.

4. The method of claim 2, wherein: the fluoronitrobenzene in the step (1) is 2-fluoro-5-nitrotoluene and 5-fluoro-2-nitrotoluene respectively, wherein the fluoronitrobenzene used for preparing the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene is 2-fluoro-5-nitrotoluene, and the fluoronitrobenzene used for preparing the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl ] fluorene is 5-fluoro-2-nitrotoluene.

5. The method of claim 2, wherein: the organic solvent in the step (1) is selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, and the mass of the organic solvent is 2-3 times of the total mass of a bisphenol compound 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene and 2-fluoro-5-nitrotoluene (or 5-fluoro-2-nitrotoluene).

6. The method of claim 2, wherein: the alkaline catalyst in the step (1) is potassium carbonate or sodium carbonate, and the mole number of the alkaline catalyst is 2.0-3.0 times of that of 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene of a bisphenol compound.

7. The method of claim 2, wherein: the organic solvent in the step (2) is a mixed solvent of ethanol and ethylene glycol methyl ether with the mass ratio of 1: 1.0-3.0, and the mass of the mixed solvent is 3-6 times that of the dinitro compound.

8. The method of claim 2, wherein: the catalyst in the step (2) is palladium carbon with 5 percent or 10 percent of palladium by mass, and the dosage of the catalyst is 2 to 4 percent of the mass of the dinitro compound; the reducing agent is hydrazine hydrate solution with solute mass fraction of 80%, and the dosage of the reducing agent is 4-12 times of the mole number of the dinitro compound.

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