CN104447441A - Aromatic diamine monomer simultaneously containing four lateral substituents and having twisted non-coplanar structure and preparation method thereof - Google Patents
Aromatic diamine monomer simultaneously containing four lateral substituents and having twisted non-coplanar structure and preparation method thereof Download PDFInfo
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- CN104447441A CN104447441A CN201410555775.5A CN201410555775A CN104447441A CN 104447441 A CN104447441 A CN 104447441A CN 201410555775 A CN201410555775 A CN 201410555775A CN 104447441 A CN104447441 A CN 104447441A
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Abstract
The invention provides an aromatic diamine monomer simultaneously containing four lateral substituents and having a twisted non-coplanar structure: 2,2'-di[3,5-di(4-trifluoromethylphenyl)-4-(4-aminophenoxy) phenyl] sulfone. A preparation method comprises: reacting 2,2'-di(3,5-dibromo-4-fluorophenyl) sulfone and 4-trifluoromethylphenyl boracic acid under an alkali condition in the presence of a catalyst to obtain an intermediate difluoride, further reacting the intermediate difluoride and 4-aminophenol under an alkali condition, and purifying a crude product to obtain the aromatic diamine monomer containing big tetra (4-trifluoromethyl) phenyl lateral substituents. The diamine monomer, which simultaneously contains a few big lateral substituents and has a highly twisted non-coplanar structure, can be applied to preparation of high-performance polyimide gas separation membrane materials.
Description
Technical field
The invention belongs to aromatic diamine monomers and preparation field thereof, particularly a kind ofly replace greatly aromatic diamine monomers of side bases and distortion non-co-planar structure and preparation method thereof containing four simultaneously.
Background technology
Polyimide is the high-temperature polymer that a class contains five yuan of imide ring structures, owing to having excellent thermal characteristics, mechanical property and electric property, and can as high-temperature-resistant structure material, gas separation membrane material, microelectronic packaging material etc.When using as gas separation membrane material, there is shaping filming technology complexity, the not high deficiency of gas separating property in commercialization polyimide mostly.For meeting the needs of efficient gas separating device development, design and modification polyimide molecule structure, film forming properties and the gas separating property of improving polyimide further have important researching value.
Research finds, by introducing the replacement side base of large free volume in polyimide molecule structure, can improve the performance of polyimide preferably.Aromatic diamine monomers containing large replacement side based structures is the key monomer preparing polyimide gas separating film material, but the synthesis of such monomer exists larger difficulty usually, usually needs polystep reaction to complete.That has reported at present only replaces side base containing 1-2 large volume usually containing the aromatic diamine monomers and polyimide thereof that replace greatly side based structures, rare aromatic diamine monomers and the polyimide thereof simultaneously containing multiple large replacement sides based structures.
Summary of the invention
The object of the invention is to utilize relatively easy synthetic route and conventional organic reaction, report and a kind ofly replace greatly aromatic diamine monomers of side bases and distortion non-co-planar structure and preparation method thereof containing four simultaneously; This diamine monomer can be used for preparing high-performance polyimide gas separation membrane material.
Patent of the present invention contains four aromatic diamine monomers replacing greatly side bases and distortion non-co-planar structure while reporting be 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone, and its structural formula is
This aromatic diamine monomers is white powdery solids, and fusing point is respectively at 261 ~ 262 DEG C.
Present invention also offers a kind of preparation method of above-mentioned aromatic diamine monomers, concrete steps are as follows:
(1) under nitrogen protection; be 2 of 1:4.0 ~ 4.4 by mol ratio; 2 '-bis-(3; the bromo-4-fluorophenyl of 5-bis-) sulfone and 4-trifluoromethylbenzene boronic acid join in there-necked flask; add organic solvent, water, catalyzer and alkaline matter respectively again; after stirred at ambient temperature is even; under being warming up to reflux state; continue reaction 8 ~ 16h; further by organic solvent evaporate to dryness, crude product is recrystallization after suction filtration, drying, obtains intermediate double fluorine cpd 2; 2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone.
Wherein, catalyzer is tetrakis triphenylphosphine palladium, and its consumption is 4% ~ 6% times of the amount of substance of 2,2 '-bis-(the bromo-4-fluorophenyl of 3,5-bis-) sulfone; Alkaline matter is sodium carbonate, and its consumption is 8 ~ 10 times of the amount of substance of 2,2 '-bis-(the bromo-4-fluorophenyl of 3,5-bis-) sulfone; The consumption of water is 4 ~ 5 times of sodium carbonate quality; Organic solvent is the toluene of volume ratio 1:1 and the mixed solvent of glycol dimethyl ether, and the consumption of organic solvent is 1.0 ~ 1.2 times of volume of water.
(2) under nitrogen protection; be obtain in the step (1) of 1:2.0 ~ 2.2 2 by mol ratio; 2 '-bis-[3; 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone and PAP be dissolved in organic solvent; 110 ~ 140 DEG C of reaction 8 ~ 12h in the basic conditions; terminating reaction pours in ice-water bath by reactant; separate out a large amount of pressed powder; crude product is recrystallization after suction filtration, drying; namely diamine monomer 2 is obtained; 2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone.
Wherein, organic solvent is selected from DMF, N, N-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, its consumption be 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone and PAP total mass and 2 ~ 4 times; Alkaline condition is that salt of wormwood is dissolved in the alkaline system formed in organic solvent, and its consumption is 1.0 ~ 1.3 times of PAP mole number.Concrete synthetic route is as follows:
The invention has the beneficial effects as follows:
(1) the invention provides one and replace side base and distortion non-co-planar structure aromatic diamine monomers and preparation method thereof greatly containing four simultaneously, its synthetic route is simple, and product is easy to purification & isolation, stable under normal temperature; And while the base of multiple large replacement sides, introduce the free volume that not only can increase polymer molecular chain further, molecular chain structure can also be made to present distortion non-co-planar structure, and this molecular characterization better can improve the gas separating property of polyimide film material;
(2) with the preparation that can be used for high-performance polyimide gas separation membrane material containing four large replacement side bases and distortion non-co-planar structure aromatic diamine monomers provided by the invention simultaneously, replace side base greatly containing four in prepared polyimide polymer molecular chain structure unit simultaneously, there is large free volume and high distortion non-co-planar structure;
(3) by the polyimide film material contained prepared by four (4-trifluoromethyl) benzene large replacement side based structures aromatic diamine monomers provided by the invention, there is excellent gas separating property, good thermostability and film-forming properties, in efficient gas separating device field, there is potential using value.
Accompanying drawing explanation
Fig. 1 is in embodiment 1, the infared spectrum of 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone.
Fig. 2 is in embodiment 1,2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone
1h NMR collection of illustrative plates.
Fig. 3 is in the present invention, spatial configuration of molecules the lowest energy conformation figure of 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone.
Embodiment
The preparation of 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone:
Embodiment 1
(1) mechanical stirring is being housed, in the there-necked flask of the 1000ml of condensing works and nitrogen protection, add 2 of 28.492g (0.05mol) respectively, 2 '-bis-(3, the bromo-4-fluorophenyl of 5-bis-) the 4-trifluoromethylbenzene boronic acid of sulfone and 37.986g (0.20mol), the tetrakis triphenylphosphine palladium of 2.311g (0.002mol), the sodium carbonate of 42.396g (0.40mol), the water of 170g, 85ml toluene and 85ml glycol dimethyl ether, after stirring 10min under room temperature (25 DEG C), under being warming up to reflux state, after reaction 8h, steam organic solvent, crude product is through suction filtration, washing, after drying, utilize N, the further recrystallization of dinethylformamide, obtain white powder intermediate double fluorine cpd 2, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone, productive rate is 81% (by 2, 2 '-bis-(3, the bromo-4-fluorophenyl of 5-bis-) sulfone transformation efficiency calculate).
The fusing point of above-mentioned 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-fluorophenyl] obtained sulfone is 315 ~ 316 DEG C (tested by DSC and obtain, temperature rise rate 10 DEG C/min).
FT-IR(KBr)ν/cm
-1:2926,1329,1168,1120.
1H NMR(CDCl
3,400MHz)δ:8.07(d,J＝6.3Hz,4H),7.76(d,J＝8.3Hz,8H),7.67(d,J＝8.0Hz,8H).
(2) mechanical stirring is being housed, in the there-necked flask of the 250ml of condensing works and nitrogen protection, add obtain in the step (1) of 41.532g (0.05mol) 2 respectively, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone, the PAP of 10.913g (0.10mol), the salt of wormwood of 13.821g (0.10mol) and the N of 105g, dinethylformamide, at 140 DEG C after stirring reaction 8h, terminating reaction pours in ice-water bath by reactant, separate out a large amount of pressed powder, crude product is through suction filtration, after drying, further spent glycol methyl ether recrystallization, obtain the diamine monomer of white, productive rate is 75% (by 2, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone transformation efficiency calculate).
Wherein, the fusing point of 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone obtained in the present embodiment is 261 ~ 262 DEG C (tested by DSC and obtain, temperature rise rate 10 DEG C/min).FT-IR (KBr) ν/cm
-1: 3300-3600,1624,1509,1329,1122,1064.
1h NMR (CDCl
3, 400MHz) and δ: 8.04 (s, 4H), 7.26 (s, 16H), 6.27 (d, J=8.6Hz, 4H), 6.20 (d, J=8.7Hz, 4H), 3.31 (s, 4H). as illustrated in fig. 1 and 2.
Embodiment 2
(1) mechanical stirring is being housed, in the there-necked flask of the 1000ml of condensing works and nitrogen protection, add 2 of 28.492g (0.05mol) respectively, 2 '-bis-(3, the bromo-4-fluorophenyl of 5-bis-) the 4-trifluoromethylbenzene boronic acid of sulfone and 41.785g (0.22mol), the tetrakis triphenylphosphine palladium of 3.466g (0.003mol), the sodium carbonate of 52.995g (0.50mol), the water of 265g, 158ml toluene and 158ml glycol dimethyl ether, after stirring 10min under room temperature (25 DEG C), under being warming up to reflux state, after reaction 16h, steam organic solvent, crude product is through suction filtration, washing, after drying, utilize N, the further recrystallization of dinethylformamide, obtain white powder intermediate double fluorine cpd 2, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone, productive rate is 82% (by 2, 2 '-bis-(3, the bromo-4-fluorophenyl of 5-bis-) sulfone transformation efficiency calculate).
(2) mechanical stirring is being housed, in the there-necked flask of the 250ml of condensing works and nitrogen protection, add obtain in the step (1) of 41.532g (0.05mol) 2 respectively, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone, the PAP of 12.004g (0.11mol), the salt of wormwood of 19.764g (0.143mol) and the N of 214g, dinethylformamide, at 110 DEG C after stirring reaction 12h, terminating reaction pours in ice-water bath by reactant, separate out a large amount of pressed powder, crude product is through suction filtration, after drying, further spent glycol methyl ether recrystallization, obtain the diamine monomer of white, productive rate is 74% (by 2, 2 '-bis-[3, 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone transformation efficiency calculate).
Claims (6)
1. one kind replaces greatly the aromatic diamine monomers of side base and distortion non-co-planar structure simultaneously containing four, it is characterized in that: described diamine monomer is 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone, its structural formula is
2. aromatic diamine monomers as claimed in claim 1, is characterized in that: described aromatic diamine monomers contains sulfobenzide structure, and simultaneously containing four 4-trifluoromethylbenzene large replacement side bases in sulfobenzide structure.
3. aromatic diamine monomers as claimed in claim 1, it is characterized in that: in described aromatic diamine monomers, between two phenyl ring be connected between two phenyl ring be connected with ehter bond and with sulfuryl, because large volume replaces the repulsive interaction between the base of side, all there is high distortion non-co-planar structure.
4. the preparation method of aromatic diamine monomers as claimed in claim 1, is characterized in that: the concrete steps of described preparation method are
(1) under nitrogen protection, be 2 of 1:4.0 ~ 4.4 by mol ratio, 2 '-bis-(3, the bromo-4-fluorophenyl of 5-bis-) sulfone and 4-trifluoromethylbenzene boronic acid join in there-necked flask, add organic solvent, water, catalyzer and alkaline matter respectively again, after stirred at ambient temperature is even, under being warming up to reflux state, continue reaction 8 ~ 16h, further by organic solvent evaporate to dryness, crude product is recrystallization after suction filtration, drying, obtains intermediate double fluorine cpd 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone;
(2) under nitrogen protection; be obtain in the step (1) of 1:2.0 ~ 2.2 2 by mol ratio; 2 '-bis-[3; 5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone and PAP be dissolved in organic solvent; 110 ~ 140 DEG C of reaction 8 ~ 12h in the basic conditions; terminating reaction pours in ice-water bath by reactant; separate out a large amount of pressed powder; crude product is recrystallization after suction filtration, drying; namely diamine monomer 2 is obtained; 2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-(4-amino-benzene oxygen) phenyl] sulfone.
5. the preparation method of aromatic diamine monomers as claimed in claim 2, it is characterized in that: the catalyzer described in step (1) is tetrakis triphenylphosphine palladium, its consumption is 2,4% ~ 6% times of the amount of substance of 2 '-bis-(the bromo-4-fluorophenyl of 3,5-bis-) sulfone; Described alkaline matter is sodium carbonate, and its consumption is 8 ~ 10 times of the amount of substance of 2,2 '-bis-(the bromo-4-fluorophenyl of 3,5-bis-) sulfone; The consumption of described water is 4 ~ 5 times of sodium carbonate quality; Described organic solvent is the toluene of volume ratio 1:1 and the mixed solvent of glycol dimethyl ether, and the consumption of organic solvent is 1.0 ~ 1.2 times of volume of water.
6. the preparation method of aromatic diamine monomers as claimed in claim 2, it is characterized in that: the organic solvent described in step (2) is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, its consumption is 2,2 '-bis-[3,5-bis-(4-trifluoromethyl)-4-fluorophenyl] sulfone and PAP total mass and 2 ~ 4 times; Described alkaline condition is that salt of wormwood is dissolved in the alkaline system formed in organic solvent, and salt of wormwood consumption is 1.0 ~ 1.3 times of PAP mole number.
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Cited By (4)
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| CN107854973A (en) * | 2017-10-09 | 2018-03-30 | 青岛大学 | A kind of Noryl gas separation membrane and preparation method |
| CN108358795A (en) * | 2018-03-15 | 2018-08-03 | 常州大学 | One kind is containing tertiary butyl substitution m-Terphenyl structure aromatic diamine monomers and preparation method thereof |
| CN113490543A (en) * | 2019-02-28 | 2021-10-08 | 富士胶片株式会社 | Polymer and method for producing same, gas separation membrane, gas separation module, and gas separation device using same, and m-phenylenediamine compound |
| US11806661B2 (en) | 2019-02-28 | 2023-11-07 | Fujifilm Corporation | Polymer and method for producing the same, gas separation membrane, gas separation module, and gas separation apparatus using the polymer, and m-phenylenediamine compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107854973A (en) * | 2017-10-09 | 2018-03-30 | 青岛大学 | A kind of Noryl gas separation membrane and preparation method |
| CN107854973B (en) * | 2017-10-09 | 2021-04-23 | 青岛大学 | Modified polyphenyl ether gas separation membrane and preparation method thereof |
| CN108358795A (en) * | 2018-03-15 | 2018-08-03 | 常州大学 | One kind is containing tertiary butyl substitution m-Terphenyl structure aromatic diamine monomers and preparation method thereof |
| CN108358795B (en) * | 2018-03-15 | 2020-03-20 | 常州大学 | Aromatic diamine monomer containing tert-butyl substituted meta-terphenyl structure and preparation method thereof |
| CN113490543A (en) * | 2019-02-28 | 2021-10-08 | 富士胶片株式会社 | Polymer and method for producing same, gas separation membrane, gas separation module, and gas separation device using same, and m-phenylenediamine compound |
| US11806661B2 (en) | 2019-02-28 | 2023-11-07 | Fujifilm Corporation | Polymer and method for producing the same, gas separation membrane, gas separation module, and gas separation apparatus using the polymer, and m-phenylenediamine compound |
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Application publication date: 20150325 |