CN103483206A - Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer - Google Patents
Diamine monomer containing asymmetric and non-coplanar structure, and preparation method of diamine monomer Download PDFInfo
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- CN103483206A CN103483206A CN201310448514.9A CN201310448514A CN103483206A CN 103483206 A CN103483206 A CN 103483206A CN 201310448514 A CN201310448514 A CN 201310448514A CN 103483206 A CN103483206 A CN 103483206A
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- diamine monomer
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Abstract
The invention discloses diamine monomer containing an asymmetric and non-coplanar structure, and a preparation method of diamine monomer. The structural general formula of the diamine monomer containing the asymmetric and non-coplanar structure is shown in the specification, wherein R represents an alkyl substituent, and Ar represents an aromatic substituent; under nitrogen protection, 2-alkyl substituted aniline and aromatic substitution substituted formaldehyde are heated, in an acidic condition, to obtain a crude product; the obtained crude product is further subject to purification through the silica column chromatography separation method, so that the diamine monomer containing the asymmetric and non-coplanar structure is obtained. The diamine monomer prepared through the invention has a high purity, is stable at normal temperature, has a simple synthesis method, and is suitable for industrial production; the obtained monomer has the asymmetric and non-coplanar structure, so that the prepared poly imide has excellent solubility, excellent thermostability, high optical transparency, low dielectric constant, and other excellent comprehensive properties.
Description
Technical field
The invention belongs to aromatic diamine monomers and preparing technical field thereof, particularly a kind of diamine monomer containing asymmetric non-coplanar structure and preparation method thereof.
Background technology
The polyimide material thermal stability excellent with it, mechanical property, dielectric properties, chemical proofing, erosion resistance etc. are widely used in the high-tech areas such as aerospace, machinery, electronics, automobile.Due to the stiff backbone structure of polyimide uniqueness, make most of polyimide there is the shortcomings such as higher processing temperature, insoluble molten, poor processability, thereby further limit their widespread uses in association area.In order to meet the growth requirement of modern high-tech field, overcome the above-mentioned shortcoming of polyimide material, prepare the interest that solubility property is good, the polyimide material of excellent combination property more and more causes researcher.
The research of at present relevant soluble polyimide is a lot, and wherein the most effectively one of means are to introduce containing fluoro substituents in diamines.Reported diamine derivative of a kind of fluorinated aromatic pendant and preparation method thereof (CN1970527) such as people such as Yang Shiyong; Wang claims meaning to wait the people to synthesize a kind of bis trifluoromethyl that contains and replaces asymmetric aromatic diamine monomers and preparation method thereof (CN102796015); The people such as Li Yanfeng have studied a kind of fluorine-containing asymmetric directivity ether diamine and preparation and application (CN1821215).Above-mentioned fluorochemical monomer all can be used for the synthetic of soluble polyimide, but the raw material of these fluorinated diamine monomers is expensive, synthetic route more complicated and the factor such as comparatively difficult of purifying, and has further limited its application.
In recent years, researcher is incorporated into non-coplanar structure in polyimide structures and prepares soluble polyimide by molecular designing.Owing to containing large substituted aroma side group in such polymer molecule main chain, the gained polyimide material at room temperature not only can be dissolved in high bp polar solvent fully, as DMF, DMAc, NMP,
m-Cresol etc., even can also be dissolved in low boiling point solvent, as CDCl
3, THF and acetone etc.This class material also has thermal characteristics, optical property and dielectric properties etc. preferably simultaneously.Aspect thermal characteristics, with commercial polyimide, compare, although reduced to a certain extent the thermostability of polyimide, be enough to meet its service requirements in the Application Areass such as microelectronics, photoelectron.
Summary of the invention
The purpose of this invention is to provide a kind of diamine monomer containing asymmetric non-coplanar structure and preparation method thereof.
Reaction equation of the present invention is:
The structural formula general formula of the diamine monomer containing asymmetric non-coplanar structure of the present invention is:
Wherein R is a kind of in following 7 kinds of alkyl structure formulas:
Ar is a kind of in following 9 kinds of aromatic structure formulas:
The preparation method of the above-mentioned diamine monomer containing asymmetric non-coplanar structure is:
(1) hydrochloric acid that the fragrance of 20 ~ 40 amount of substance parts is replaced to formaldehyde and 10 ~ 20 amount of substance parts evenly mixes, and makes mixed solution.
(2) under nitrogen protection, the 2-alkyl substituted benzene amine of 100 amount of substance parts is warming up to 110 ~ 120 ℃, then be added dropwise to whole mixed solutions that step (1) makes in 1 ~ 1.5 hour, dropwise rear lasting stirring 30 minutes, being warming up to 150 ~ 160 ℃ refluxes 10 ~ 12 hours again, then be cooled to 60 ℃, progressively be added dropwise to alkaline solution and be neutralized to neutrality, after continuing to be cooled to room temperature, first add organic solvent extraction, use again distilled water wash 3 ~ 4 times, then with anhydrous sodium sulfate drying, spend the night, filter, revolve and steam except desolventizing, the crude product obtained is further purified by the silica gel column chromatography partition method, finally obtain the diamine monomer containing asymmetric non-coplanar structure.
Described 2-alkyl substituted benzene amine is a kind of in 2-aminotoluene, 2-ethylaniline, 2-propyl group aniline, 2-isopropyl aniline, 2-butylaniline, 2-isobutyl-aniline and 2-tertiary butyl aniline.
It is a kind of in 4-ethylbenzene formaldehyde, 4-propylbenzene formaldehyde, 4-isopropyl benzene formaldehyde, 4-butyl benzaldehyde, 4-isobutyl-benzene formaldehyde, 4-tert.-butylbenzene formaldehyde, 1-naphthaldehyde, 2-naphthaldehyde and 9-anthraldehyde that described fragrance replaces formaldehyde.
The concentrated hydrochloric acid that described hydrochloric acid is 12 N.
Described alkaline solution is the aqueous sodium hydroxide solution that mass percent concentration is 10%.
Described organic solvent is a kind of in methylene dichloride, ethyl acetate and sherwood oil.
Advantage of the present invention is:
(1) the diamine monomer purity containing asymmetric non-coplanar structure that prepared by the present invention is high, stable under normal temperature.
(2) preparation method of the present invention is simple to operate, with low cost, simultaneously to conversion unit without particular requirement, be applicable to suitability for industrialized production.
(3) while preparing polyimide, introducing due to the asymmetric non-coplanar structure of rigidity, such material, when maintaining superior thermal stability and mechanical property, also improves the solubility property, optical property, dielectric properties of polyimide material and low rate of moisture absorption etc. greatly.
The accompanying drawing explanation
The structural formula general formula that Fig. 1 is the diamine monomer containing asymmetric non-coplanar structure of the present invention.
The structural formula of 3,3 ˊ that Fig. 2 is the embodiment of the present invention 1 preparation-di-t-butyl-4,4 ˊ-diamino-phenyl-4 〞-4-tert-butyltoluene.
The structural formula of 3,3 ˊ that Fig. 3 is the embodiment of the present invention 2 preparations-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane.
The FT-IR of 3,3 ˊ that Fig. 4 is the embodiment of the present invention 1 preparation-di-t-butyl-4,4 ˊ-diamino-phenyl-4 〞-4-tert-butyltoluene.
3,3 ˊ that Fig. 5 is the embodiment of the present invention 1 preparation-di-t-butyl-4,4 ˊ-diamino-phenyl-4 〞-4-tert-butyltoluene
1h NMR.
The FT-IR of 3,3 ˊ that Fig. 6 is the embodiment of the present invention 2 preparations-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane.
3,3 ˊ that Fig. 7 is the embodiment of the present invention 2 preparations-di-t-butyl-4,4 ˊ-diamino-phenyl-1-naphthalene methane
1h NMR.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should understand, these embodiment only are not used in and limit the scope of the invention for the present invention is described, should understand in addition, after the content of having read the present invention's instruction, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1:
(1) hydrochloric acid that is 12 N by 6.5 grams (0.040 mole) 4-tert.-butylbenzene formaldehyde and 1.5 ml concns evenly mixes, and makes mixed solution.
(2) under nitrogen protection, 15 grams (0.100 mole) 2-tertiary butyl aniline is warming up to 120 ℃, then be added dropwise to whole mixed solutions that step (1) makes in 1 hour, dropwise rear lasting stirring 30 minutes, being warming up to 160 ℃ refluxes 10 hours again, then be cooled to 60 ℃, the aqueous sodium hydroxide solution that progressively to be added dropwise to mass percent concentration be 10% is to be neutralized to neutrality, after continuing to be cooled to room temperature, first add dichloromethane extraction, use again distilled water wash 3 times, then with anhydrous sodium sulfate drying, spend the night, filter, revolve and steam except desolventizing, the crude product obtained is further with silica gel column chromatography partition method purification (leacheate is ethyl acetate and the sherwood oil mixed solution that volume ratio is 1:8), finally obtain pale yellow powder shape solid and be the diamine monomer (3 containing asymmetric non-coplanar structure, 3 ˊ-di-t-butyl-4, 4 ˊ-diamino-phenyl-4 〞-4-tert-butyltoluene).
Productive rate in the present embodiment is about 65%; Fusing point is 27.2 ℃ (by DSC, recording); FT-IR (KBr, cm
-1): 3390 ~ 3445(-NH
2), 2961,2868(C-H), 1621,1506,1499,1384,489;
1h NMR (δ, ppm, DMSO): 7.28 (d, 2H, J=8.0 Hz), 7.02 (d, 2H, J=8.0 Hz), (6.90 s, 2H), 6.65 (d, 2H, J=6.8 Hz), 6.56 (d, 2H, J=7.6 Hz), 5.12 (s, H), 4.59 (s, 4H, NH
2), 1.27 (d, 27H, J=4.8Hz).
13c NMR (δ, ppm, DMSO): 148.31,144.40,143.69,133.17,132.26,129.08,127.59,127.27,125.31,117.54,55.72,34.61,31.93,29.98.
embodiment 2:
(1) hydrochloric acid that is 12 N by 6.0 grams (0.038 mole) 1-naphthaldehyde and 1.5 ml concns evenly mixes, and makes mixed solution.
(2) under nitrogen protection, 15 grams (0.100 mole) 2-tertiary butyl aniline is warming up to 110 ℃, then be added dropwise to whole mixed solutions that step (1) makes in 1.5 hours, dropwise rear lasting stirring 30 minutes, being warming up to 150 ℃ refluxes 12 hours again, then be cooled to 60 ℃, the aqueous sodium hydroxide solution that progressively to be added dropwise to mass percent concentration be 10% is to be neutralized to neutrality, after continuing to be cooled to room temperature, first add dichloromethane extraction, use again distilled water wash 4 times, then with anhydrous sodium sulfate drying, spend the night, filter, revolve and steam except desolventizing, the crude product obtained is further with silica gel column chromatography partition method purification (leacheate is ethyl acetate and the sherwood oil mixed solution that volume ratio is 1:6), finally obtain the white powder solid and be the diamine monomer (3 containing asymmetric non-coplanar structure, 3 ˊ-di-t-butyl-4, 4 ˊ-diamino-phenyl-1-naphthalene methane).
Productive rate in the present embodiment is about 75%; Fusing point is 40.2 ℃ (by DSC, recording); FT-IR (KBr, cm
-1): 3386 ~ 3454 cm
-1(NH
2), 2963 ~ 2869 cm
-1(C-H), 1618,1466,1245,787;
1h NMR (
δ, ppm, DMSO): 8.15 (d, 1H, J=7.2 Hz), (7.90 d, 1H, J=7.6 Hz), 7.75 (s, 1H, J=8.0 Hz), 7.45 (m, 3H, J=19.6 Hz), 6.98 (d, 1H, J=7.2 Hz), 6.90 (s, 2H), 6.65 (d, 2H, J=7.6 Hz), 6.56 (d, 2H, J=8.0 Hz), (5.99 s, 1H), 4.61 (s, 4H ,-NH
2), 1.24 (s, 18H ,-CH
3);
13c NMR (δ, ppm, DMSO): 144.540,142.747,134.219,132.592,132.395,132.227,129.1126,127.895,127.591,127.029,126.436,125.964,125.873,125.144,117.604,51.949,3 4.620,29.999.
Claims (2)
1. the diamine monomer containing asymmetric non-coplanar structure is characterized in that the structural formula general formula of the described diamine monomer containing asymmetric non-coplanar structure is:
Wherein R is a kind of in following 7 kinds of alkyl structure formulas:
Ar is a kind of in following 9 kinds of aromatic structure formulas:
2. the preparation method of the diamine monomer containing asymmetric non-coplanar structure according to claim 1 is characterized in that concrete steps are:
(1) hydrochloric acid that the fragrance of 20 ~ 40 amount of substance parts is replaced to formaldehyde and 10 ~ 20 amount of substance parts evenly mixes, and makes mixed solution;
(2) under nitrogen protection, the 2-alkyl substituted benzene amine of 100 amount of substance parts is warming up to 110 ~ 120 ℃, then be added dropwise to whole mixed solutions that step (1) makes in 1 ~ 1.5 hour, dropwise rear lasting stirring 30 minutes, being warming up to 150 ~ 160 ℃ refluxes 10 ~ 12 hours again, then be cooled to 60 ℃, progressively be added dropwise to alkaline solution and be neutralized to neutrality, after continuing to be cooled to room temperature, first add organic solvent extraction, use again distilled water wash 3 ~ 4 times, then with anhydrous sodium sulfate drying, spend the night, filter, revolve and steam except desolventizing, the crude product obtained is further purified by the silica gel column chromatography partition method, finally obtain the diamine monomer containing asymmetric non-coplanar structure,
Described 2-alkyl substituted benzene amine is any in 2-aminotoluene, 2-ethylaniline, 2-propyl group aniline, 2-isopropyl aniline, 2-butylaniline, 2-isobutyl-aniline and 2-tertiary butyl aniline;
It is any in 4-ethylbenzene formaldehyde, 4-propylbenzene formaldehyde, 4-isopropyl benzene formaldehyde, 4-butyl benzaldehyde, 4-isobutyl-benzene formaldehyde, 4-tert.-butylbenzene formaldehyde, 1-naphthaldehyde, 2-naphthaldehyde and 9-anthraldehyde that described fragrance replaces formaldehyde;
The concentrated hydrochloric acid that described hydrochloric acid is 12 N;
Described alkaline solution is the aqueous sodium hydroxide solution that mass percent concentration is 10%;
Described organic solvent is a kind of in methylene dichloride, ethyl acetate and sherwood oil.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
| CN104387586A (en) * | 2014-11-11 | 2015-03-04 | 桂林理工大学 | Soluble transparent fluorine-containing polyimide material and preparation method thereof |
| CN104447351A (en) * | 2014-11-11 | 2015-03-25 | 桂林理工大学 | Fluorine-containing diamine monomer with large side group and non-coplanar structure and preparation method of fluorine-containing diamine monomer |
| CN104927054A (en) * | 2015-06-29 | 2015-09-23 | 桂林理工大学 | Soluble polyimide comprising tertiary butyl and morpholinyl structure and preparation method of soluble polyimide |
| CN105017532A (en) * | 2015-06-29 | 2015-11-04 | 桂林理工大学 | Polyimide containing tertiary butyl and octadecyloxy structures, and preparation method thereof |
| CN106831447A (en) * | 2016-12-05 | 2017-06-13 | 中山大学 | How alkyl-substituted diamine compound of a kind of structure containing condensed-nuclei aromatics and its preparation method and application |
| CN109438254A (en) * | 2018-10-29 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of the diphenylmethane series diamines and polyamines of low big molecular impurity content |
| CN113651701A (en) * | 2021-08-16 | 2021-11-16 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance aromatic diamine organic matter and preparation method thereof |
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| CN101445484A (en) * | 2008-12-23 | 2009-06-03 | 东华大学 | Aromatic diamines monomer with double miscellaneous naphthalenone structures and trifluoromethyl substituted and preparation thereof |
| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| CN101659617A (en) * | 2009-09-10 | 2010-03-03 | 华东理工大学 | Preparation method of alky-substituted aromatic diamine |
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| CN101445484A (en) * | 2008-12-23 | 2009-06-03 | 东华大学 | Aromatic diamines monomer with double miscellaneous naphthalenone structures and trifluoromethyl substituted and preparation thereof |
| CN101514164A (en) * | 2009-04-03 | 2009-08-26 | 东华大学 | Polyalkyl-substituted aromatic diamine monomer and preparation and application thereof |
| CN101659617A (en) * | 2009-09-10 | 2010-03-03 | 华东理工大学 | Preparation method of alky-substituted aromatic diamine |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
| CN104387586A (en) * | 2014-11-11 | 2015-03-04 | 桂林理工大学 | Soluble transparent fluorine-containing polyimide material and preparation method thereof |
| CN104447351A (en) * | 2014-11-11 | 2015-03-25 | 桂林理工大学 | Fluorine-containing diamine monomer with large side group and non-coplanar structure and preparation method of fluorine-containing diamine monomer |
| CN104927054A (en) * | 2015-06-29 | 2015-09-23 | 桂林理工大学 | Soluble polyimide comprising tertiary butyl and morpholinyl structure and preparation method of soluble polyimide |
| CN105017532A (en) * | 2015-06-29 | 2015-11-04 | 桂林理工大学 | Polyimide containing tertiary butyl and octadecyloxy structures, and preparation method thereof |
| CN104927054B (en) * | 2015-06-29 | 2017-06-30 | 桂林理工大学 | Soluble polyimide containing the tert-butyl group and morpholine based structures and preparation method thereof |
| CN106831447A (en) * | 2016-12-05 | 2017-06-13 | 中山大学 | How alkyl-substituted diamine compound of a kind of structure containing condensed-nuclei aromatics and its preparation method and application |
| CN109438254A (en) * | 2018-10-29 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of the diphenylmethane series diamines and polyamines of low big molecular impurity content |
| CN109438254B (en) * | 2018-10-29 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of diphenylmethane series diamine and polyamine with low macromolecular impurity content |
| CN113651701A (en) * | 2021-08-16 | 2021-11-16 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance aromatic diamine organic matter and preparation method thereof |
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