CN100460390C - Bi(N-methylphthalic imidine) ester preparation method - Google Patents
Bi(N-methylphthalic imidine) ester preparation method Download PDFInfo
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- CN100460390C CN100460390C CNB2007100368742A CN200710036874A CN100460390C CN 100460390 C CN100460390 C CN 100460390C CN B2007100368742 A CNB2007100368742 A CN B2007100368742A CN 200710036874 A CN200710036874 A CN 200710036874A CN 100460390 C CN100460390 C CN 100460390C
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Abstract
The invention discloses a making method of di (N-methyl phthaloyl imine) ether, which comprises the following steps: proceeding self-condensing reaction for N-4-nitro phthaloyl imine in the polar non-proton solvent under composite catalyst and normal pressure; heating to reflux 6-8h; filtering; cooling; evolving product; washing; drying to recycle solvent; obtaining the composite catalyst with gas-phased silica, sodium carbonate and phase-transmitting catalyst.
Description
Technical field
The present invention relates to a kind of in the position 1 and 3 heterogeneous ring compounds that Sauerstoffatom arranged, more particularly relate to a kind of preparation method of two (N-methyl phthalimide) ethers.
Background technology
ODPA is one of important monomer for preparing fire resistant resins such as ANALYSIS OF MOLDABLE POLYIMIDES, two (N-methyl phthalimide) ether is synthetic 3,3 ', 4, the intermediate of 4 '-diphenyl ether tetraformic dianhydride, along with China is more and more paid attention to as emphasis novel material monomer the ODPA that continually develops of polyimide novel material, the requirement of two (N-methyl phthalimide) ether also increases year by year.At present, the preparation method of two (N-methyl phthalimide) ether carries out self condensation with the nitrite of basic metal, alkaline-earth metal or with catalyzer such as Potassium monofluoride, Sodium Fluorides, the yield of two (N-methyl phthalimide) ether is lower, generally 65～75%, the yield of suitability for industrialized production is 50～60%, and solvent recovering rate is not high.Therefore, existing method is produced two (N-methyl phthalimide) ether product cost height, and three wastes treatment capacity is big, is difficult to promotion and application.
Summary of the invention
Technical problem to be solved by this invention provides the method for two (N-methyl phthalimide) ethers of preparation that a kind of production cost is low, environmental pollution is less, yield is high.
The technical solution used in the present invention: the method for two (N-methyl phthalimide) ethers of a kind of preparation, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, cool off and separate out product, after washing, drying, reclaim solvent, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is the composite catalyst that gas-phase silica, carbonate and phase-transfer catalyst mix.
The method of two (N-methyl phthalimide) ethers of a kind of preparation, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, cool off and separate out product, after washing, drying, reclaim solvent, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is the composite catalyst that gas-phase silica, yellow soda ash and phase-transfer catalyst mix.
Described phase-transfer catalyst is a Tetrabutyl amonium bromide.
The mol ratio of gas-phase silica and yellow soda ash is 30～50% in the described composite catalyst.
The mol ratio of the total amount of gas-phase silica and yellow soda ash and N-methyl in the described composite catalyst-4-nitro phthalic imidine is 0.8～1.0:1.
The mol ratio of described phase-transfer catalyst Tetrabutyl amonium bromide and N-methyl-4-nitro phthalic imidine is 0.02～0.05:1.
Beneficial effect of the present invention, the present invention has following advantage: one, production cost is lower, the yield height, quality is good.The yield of two (N-methyl phthalimide) ether products that make with the composite synergistic catalyzer is increased to 75～80% from 65～75% (suitability for industrialized production yields 50～60%), and 269～273 ℃ of fusing points have improved product amount and quality.Two, simple to operate, environmental pollution is little: carry out owing to be reflected under normal pressure and the backflow, technology is simple, and product yield improves, and solvent is easy to recovery of applied, has reduced three waste discharge.
Embodiment
Below by embodiment the present invention is described in further detail, the method of two (N-methyl phthalimide) ethers of a kind of preparation, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, product is separated out in cooling, through washing, solvent is reclaimed in dry back, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is a gas-phase silica, the composite catalyst that carbonate and phase-transfer catalyst mix.
The method of two (N-methyl phthalimide) ethers of a kind of preparation, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, cool off and separate out product, after washing, drying, reclaim solvent, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is the composite catalyst that gas-phase silica, yellow soda ash and phase-transfer catalyst mix.
Described phase-transfer catalyst is a Tetrabutyl amonium bromide.The mol ratio of gas-phase silica and yellow soda ash is 30～50% in the described composite catalyst.The mol ratio of the total amount of gas-phase silica and yellow soda ash and N-methyl in the described composite catalyst-4-nitro phthalic imidine is 0.8～1.0:1.The mol ratio of described phase-transfer catalyst Tetrabutyl amonium bromide and N-methyl-4-nitro phthalic imidine is 0.02～0.05:1.
Embodiment 1:
Agitator is being housed, condenser, (add 206 gram (1mol) N-methyl-4-nitro phthalic imidine and composite catalysts in the there-necked flask: 63.6 restrain (0.6mol) yellow soda ash to the 1000ml of thermometer, 16.2 gram (0.27mol) gas-phase silica, 8.05 gram (0.025mol) Tetrabutyl amonium bromide and 270ml dimethyl sulfoxide (DMSO), heated and stirred is to refluxing, afterreaction finished in 6 hours, filtered while hot immediately, filtrate is cooled to room temperature, separate out product, after filtration, reclaim solvent, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 127 grams, yield 75.6%, 268.5～271 ℃ of fusing points
Embodiment 2:
With embodiment 1, the adding composite catalyst is: 74.2 gram (0.7mol) yellow soda ash, gas-phase silica 14.7 grams (0.245mol), Tetrabutyl amonium bromide 14.49 gram (0.045mol) reactions 8 hours.Other condition is identical with embodiment 1.Obtain two (N-methyl phthalimide) ethers of the pale brown look of 133 grams, yield 79.2%, 269～271 ℃ of fusing points.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Other condition is identical with embodiment 1.Obtain two (N-methyl phthalimide) ethers of the pale brown look of 133 grams, yield 79.2%, 269～271 ℃ of fusing points.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. method for preparing two (N-methyl phthalimide) ethers, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, cool off and separate out product, after washing, drying, reclaim solvent, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is the composite catalyst that gas-phase silica, carbonate and phase-transfer catalyst mix.
2. method for preparing two (N-methyl phthalimide) ethers, make N-methyl-4-nitro phthalic imidine in polar aprotic solvent He under the normal pressure, carry out self condensation reaction under the composite catalyst catalysis, reflux 6～8 hours, filter then, cool off and separate out product, after washing, drying, reclaim solvent, obtain two (N-methyl phthalimide) ether products at last, wherein said composite catalyst is the composite catalyst that gas-phase silica, yellow soda ash and phase-transfer catalyst mix.
3. the method for two (N-methyl phthalimide) ethers of preparation according to claim 1 and 2, it is characterized in that: described phase-transfer catalyst is a Tetrabutyl amonium bromide.
4. the method for two (N-methyl phthalimide) ethers of preparation according to claim 2, it is characterized in that: the mol ratio of gas-phase silica and yellow soda ash is 30～50% in the described composite catalyst.
5. the method for two (N-methyl phthalimide) ethers of preparation according to claim 4, it is characterized in that: the mol ratio of the total amount of gas-phase silica and yellow soda ash and N-methyl in the described composite catalyst-4-nitro phthalic imidine is 0.8～1.0:1.
6. the method for two (N-methyl phthalimide) ethers of preparation according to claim 3, it is characterized in that: the mol ratio of described phase-transfer catalyst Tetrabutyl amonium bromide and N-methyl-4-nitro phthalic imidine is 0.02～0.05:1.
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| CNB2007100368742A CN100460390C (en) | 2007-01-26 | 2007-01-26 | Bi(N-methylphthalic imidine) ester preparation method |
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| CNB2007100368742A CN100460390C (en) | 2007-01-26 | 2007-01-26 | Bi(N-methylphthalic imidine) ester preparation method |
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| CN101007782A CN101007782A (en) | 2007-08-01 |
| CN100460390C true CN100460390C (en) | 2009-02-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101550102B (en) * | 2009-05-07 | 2010-12-01 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
| CN102199118B (en) * | 2011-03-16 | 2013-09-25 | 黑龙江省科学院石油化学研究院 | Oxo-bi(N-Methylphthalimide) synthesis method |
| CN103896822B (en) * | 2014-03-31 | 2016-02-10 | 仪征市海帆化工有限公司 | A kind of 3, the synthetic method of the two phthalic imidine of 4 '-oxo |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
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2007
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4933469A (en) * | 1988-12-16 | 1990-06-12 | General Electric Company | Method for preparing oxybisphthalimides |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
Non-Patent Citations (4)
| Title |
|---|
| 3,3',4,4'—二苯醚四甲酸二酐的合成和精制研究进展. 苏冬妹，宋刚，梁泰硕.化学与粘合，第6期. 2004 |
| 3,3',4,4'—二苯醚四甲酸二酐的合成和精制研究进展. 苏冬妹，宋刚，梁泰硕.化学与粘合，第6期. 2004 * |
| 氧代-双(N-甲基邻苯二甲酰亚胺)合成工艺研究. 黄琳，朱素萍.襄樊学院学报，第27卷第2期. 2006 |
| 氧代-双(N-甲基邻苯二甲酰亚胺)合成工艺研究. 黄琳，朱素萍.襄樊学院学报，第27卷第2期. 2006 * |
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