CN114349649A - Two aromatic diamine monomers containing both methoxyfluorene and methyl structure and preparation method thereof - Google Patents
Two aromatic diamine monomers containing both methoxyfluorene and methyl structure and preparation method thereof Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 32
- IJBYVSUZCRXTOD-UHFFFAOYSA-N 1-methoxy-9h-fluorene Chemical group C1C2=CC=CC=C2C2=C1C(OC)=CC=C2 IJBYVSUZCRXTOD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- WKJMXVNDOIZJPD-UHFFFAOYSA-N CC(C=C(C=C1)N)=C1OC(C(OC)=CC(C1(C2=CC=CC=C2C2=C1C=CC=C2)C(C=C1OC)=CC(OC)=C1OC(C=C1)=C(C)C=C1N)=C1)=C1OC Chemical compound CC(C=C(C=C1)N)=C1OC(C(OC)=CC(C1(C2=CC=CC=C2C2=C1C=CC=C2)C(C=C1OC)=CC(OC)=C1OC(C=C1)=C(C)C=C1N)=C1)=C1OC WKJMXVNDOIZJPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- ASGJAPNYDRGQIS-UHFFFAOYSA-N CC(C=C(C=C1)OC(C(OC)=CC(C2(C3=CC=CC=C3C3=C2C=CC=C3)C(C=C2OC)=CC(OC)=C2OC(C=C2)=CC(C)=C2N)=C2)=C2OC)=C1N Chemical compound CC(C=C(C=C1)OC(C(OC)=CC(C2(C3=CC=CC=C3C3=C2C=CC=C3)C(C=C2OC)=CC(OC)=C2OC(C=C2)=CC(C)=C2N)=C2)=C2OC)=C1N ASGJAPNYDRGQIS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract 9
- -1 bisphenol compound Chemical class 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 9
- XUCYJGMIICONES-UHFFFAOYSA-N 1-fluoro-2-methyl-4-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1F XUCYJGMIICONES-UHFFFAOYSA-N 0.000 claims description 8
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 claims description 8
- JHFOWEGCZWLHNW-UHFFFAOYSA-N 4-fluoro-2-methyl-1-nitrobenzene Chemical compound CC1=CC(F)=CC=C1[N+]([O-])=O JHFOWEGCZWLHNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000004642 Polyimide Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 229920001721 polyimide Polymers 0.000 abstract description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 12
- 150000002220 fluorenes Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 125000004427 diamine group Chemical group 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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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
Technical Field
The invention belongs to the field of aromatic diamine monomer compounds and preparation thereof, and particularly relates to two aromatic diamine monomers containing methoxyfluorene and methyl structure and a preparation method thereof.
Background
Polyimide and polyaramide are two important aromatic special high polymer materials and can be widely applied to the membrane separation fields of gas separation, ultrafiltration, reverse osmosis and the like as membrane materials. Polyimide and polyaramid are mainly prepared by the polycondensation of aromatic diamine, aromatic dianhydride and aromatic diacid monomer, and the structure of the monomer directly has decisive influence on the performance of the prepared polymer. The fluorene-containing aromatic diamine monomer is regarded as an important high-performance aromatic diamine monomer due to the rigid non-coplanar structure, and the introduction of the fluorene-containing non-coplanar structure can effectively improve the dissolving and film-forming properties and the film separation properties of the prepared aromatic polymer. However, the variety of fluorene-containing aromatic diamine monomers that are commercially available at present is very limited, and mainly 9, 9-bis (4-aminophenyl) fluorene and its derivatives. Therefore, the design and development of novel aromatic diamine monomer containing fluorene structure and the molecular modification thereof are expected to further improve the performance of the aromatic polymer prepared, and have important academic value and practical application value.
Based on the above, the invention intends to use bisphenol fluorene derivatives as the starting material, and two aromatic diamine monomers containing both methoxyfluorene and methyl structure are designed and prepared by two-step conventional organic reaction, and a plurality of methoxy groups and methyl groups are further introduced into the structure of the aromatic diamine monomer containing fluorene, so as to increase the space free volume of the diamine structure, and further improve the performance of the corresponding polymer film material.
Disclosure of Invention
The invention aims to provide two aromatic diamine monomers containing both methoxyfluorene and methyl structure and a preparation method thereof in order to meet social requirements and expand the variety of aromatic diamine monomers containing fluorene.
The invention aims to design and prepare two aromatic diamine monomers containing both methoxyfluorene and methyl structure through two-step conventional organic reaction, and further introduce a plurality of methoxy groups and methyl groups into the structure of the aromatic diamine monomer containing fluorene, thereby improving the space free volume of the diamine structure and expecting to further improve the performance of the corresponding polymer film material.
In order to achieve the above purpose, the present invention provides 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, through a simple synthetic route, and the chemical structural formulas thereof are respectively:
the monomer is white acicular crystal powder, and the melting points of the white acicular crystal powder are 259-260 ℃ and 262-263 ℃ respectively.
The invention also provides a preparation method of the two aromatic diamine monomers simultaneously containing methoxyfluorene and methyl structure, which 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.
Wherein the bisphenol compound containing the methoxyfluorene structure is 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene; the fluoronitrobenzene 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.
The organic solvent 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); the alkaline catalyst 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-hydroxyl) fluorene of a bisphenol compound.
(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.
Wherein the organic solvent is a mixed solvent of 1: 1.0-3.0 of ethanol and ethylene glycol monomethyl ether, and the mass of the organic solvent is 3-6 times that of the dinitro compound; the catalyst is palladium carbon with the mass fraction of palladium of 5 percent or 10 percent, 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.
The specific synthetic route of the two aromatic diamine monomers simultaneously containing methoxyfluorene and methyl structure provided by the invention is as follows:
the invention has the beneficial effects that:
(1) the two aromatic diamine monomers simultaneously containing methoxyfluorene and methyl structure and the preparation method thereof have the advantages of simple synthesis method, convenient product separation, high yield, good stability and easy industrial amplification production;
(2) the aromatic diamine monomer provided by the invention has larger free volume, and can be further condensed with aromatic dianhydride and aromatic diacid to prepare high-performance polyimide and polyaramide membrane materials.
Drawings
FIG. 1 shows the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl group in example 1]Of fluorenes1H NMR spectrum.
FIG. 2 shows the structure of the aromatic diamine 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl group in example 1]Of fluorenes1H NMR spectrum.
FIG. 3 shows the intermediate dinitro compound, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl group, of example 3]Of fluorenes1H NMR spectrum.
FIG. 4 shows the structure of the aromatic diamine 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl group in example 3]Of fluorenes1H NMR spectrum.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of two aromatic diamine monomers containing both methoxyfluorene and methyl structure comprises the following specific steps:
(1) 47.05g (0.1mol) of 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene, 31.02g (0.2mol) of 2-fluoro-5-nitrotoluene, 27.64g (0.2mol) of potassium carbonate and 170ml of N, N-dimethylformamide are respectively added into a 500ml dry three-neck flask provided with a nitrogen protection, a mechanical stirring and a condensing tube, stirred and reacted for 12 hours at 100 ℃, poured into an ice water bath for stirring and sedimentation to precipitate a large amount of solid, filtered and dried, and the crude product is further recrystallized by the N, N-dimethylformamide to obtain white crystal powder, namely the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene with the yield of 85 percent.
The dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl]Of fluorenes1H NMR(CDCl3400MHz) as shown in figure 1.
(2) 37.04g (0.05mol) of the dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene obtained in the step (1), 0.75g of 5% (by mass of palladium, the same applies hereinafter) of a palladium-carbon catalyst, and 130ml of an ethanol/ethylene glycol methyl ether mixed solvent (volume ratio 1: 3.0) are respectively added into a 500ml three-necked flask, and the mixture is heated to a reflux state under stirring; then 14ml of 80 percent (solute mass fraction, the same below) hydrazine hydrate solution is dripped in a constant pressure dropping funnel within 30min, the reflux reaction is continued for 4 hours, the palladium carbon is removed by hot filtration, the mixture is concentrated and precipitated by adding water, and the crude product is recrystallized by ethylene glycol monomethyl ether to obtain the 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl ] fluorene with the yield of 84 percent.
The diamine monomer is 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl]Of fluorenes1H NMR(CDCl3400MHz) as shown in figure 2.
Example 2
The preparation method of two aromatic diamine monomers containing both methoxyfluorene and methyl structure comprises the following specific steps:
(1) 47.05g (0.1mol) of 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene, 35.65g (0.23mol) of 2-fluoro-5-nitrotoluene, 41.46g (0.3mol) of potassium carbonate and 245ml of N-methylpyrrolidone are respectively added into a 500ml dry three-neck flask provided with a nitrogen protection, a mechanical stirring and a condensing tube, stirred and reacted for 6 hours at 150 ℃, poured into an ice water bath for stirring and sedimentation to precipitate a large amount of solid, filtered and dried, and the crude product is further recrystallized by N, N-dimethylformamide to obtain white crystal powder which is the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene with the yield of 86%.
(2) 37.04g (0.05mol) of the dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-nitrophenoxy) phenyl ] fluorene obtained in the step (1), 1.2g of 10% (by mass of palladium, the same applies hereinafter) of a palladium-carbon catalyst, and 180ml of an ethanol/ethylene glycol methyl ether mixed solvent (volume ratio is 1: 2.0) are respectively added into a 500ml three-necked flask, and the mixture is heated to a reflux state under stirring; then 30ml of 80 percent (solute mass fraction, the same below) hydrazine hydrate solution is dripped in a constant pressure dropping funnel within 30min, the reflux reaction is continued for 12 hours, the palladium carbon is removed by hot filtration, the mixture is concentrated and precipitated by adding water, and the crude product is recrystallized by ethylene glycol monomethyl ether to obtain the 9, 9-bis [3, 5-dimethoxy-4- (2-methyl-4-aminophenoxy) phenyl ] fluorene with the yield of 83 percent.
Example 3
The preparation method of two aromatic diamine monomers containing both methoxyfluorene and methyl structure comprises the following specific steps:
(1) 47.05g (0.1mol) of 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene, 31.02g (0.2mol) of 5-fluoro-2-nitrotoluene, 41.46g (0.3mol) of potassium carbonate and 180ml of N, N-dimethylacetamide are respectively added into a 500ml dry three-neck flask equipped with a nitrogen protection, a mechanical stirring and a condensing tube, stirred and reacted for 12 hours at 150 ℃, poured into an ice water bath and stirred and settled to precipitate a large amount of solid, filtered and dried, and the crude product is further recrystallized by N, N-dimethylformamide to obtain white crystal powder, namely the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl ] fluorene with the yield of 86%.
The dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl]Of fluorenes1H NMR(CDCl3400MHz) as shown in figure 3.
(2) 37.04g (0.05mol) of the dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl ] fluorene obtained in the step (1), 0.14g of 5% (by mass of palladium, the same applies hereinafter) of a palladium-carbon catalyst, and 130ml of an ethanol/ethylene glycol monomethyl ether mixed solvent (volume ratio 1: 2.0) are respectively added into a 500ml three-necked flask, and the mixture is heated to a reflux state under stirring; then 14ml of 80 percent (solute mass fraction, the same below) hydrazine hydrate solution is dripped in a constant pressure dropping funnel within 30min, the reflux reaction is continued for 10 hours, the palladium carbon is removed by hot filtration, the mixture is concentrated and precipitated by adding water, and the crude product is recrystallized by ethylene glycol monomethyl ether to obtain the 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl ] fluorene with the yield of 84 percent.
The above 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl group]Of fluorenes1H NMR(DMSO-d6400MHz) as shown in figure 4.
Example 4
The preparation method of two aromatic diamine monomers containing both methoxyfluorene and methyl structure comprises the following specific steps:
(1) 47.05g (0.1mol) of 9, 9-bis (3, 5-dimethoxy-4-hydroxy) fluorene, 35.65g (0.23mol) of 5-fluoro-2-nitrotoluene, 27.64g (0.2mol) of potassium carbonate and 180ml of N-methylpyrrolidone are respectively added into a 500ml dry three-neck flask provided with a nitrogen protection, a mechanical stirring and a condensing tube, stirred and reacted for 6 hours at 150 ℃, poured into an ice water bath for stirring and sedimentation to precipitate a large amount of solid, filtered and dried, and the crude product is further recrystallized by N, N-dimethylformamide to obtain white crystal powder, namely the intermediate dinitro compound 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-nitrophenoxy) phenyl ] fluorene with the yield of 84%.
(2) 37.04g (0.05mol) of the dinitro compound obtained in step (1), 0.8g of 10% (by mass) palladium on carbon catalyst, and 200ml of an ethanol/ethylene glycol methyl ether mixed solvent (in a volume ratio of 1: 2.0) were added to a 500ml three-necked flask, respectively, and the mixture was heated to reflux with stirring; then 20ml of 80 percent (solute mass fraction, the same below) hydrazine hydrate solution is dripped in a constant pressure dropping funnel within 30min, the reflux reaction is continued for 4 hours, the palladium carbon is removed by hot filtration, the mixture is concentrated and precipitated by adding water, and the crude product is recrystallized by ethylene glycol monomethyl ether to obtain the 9, 9-bis [3, 5-dimethoxy-4- (3-methyl-4-aminophenoxy) phenyl ] fluorene with the yield of 83 percent.
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:
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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