CN101550102B - Method for preparing di-(N-methyl phthalimide) ether - Google Patents
Method for preparing di-(N-methyl phthalimide) ether Download PDFInfo
- Publication number
- CN101550102B CN101550102B CN2009100223988A CN200910022398A CN101550102B CN 101550102 B CN101550102 B CN 101550102B CN 2009100223988 A CN2009100223988 A CN 2009100223988A CN 200910022398 A CN200910022398 A CN 200910022398A CN 101550102 B CN101550102 B CN 101550102B
- Authority
- CN
- China
- Prior art keywords
- methyl
- solvent
- ether
- phthalimide
- aprotic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Indole Compounds (AREA)
Abstract
The invention discloses a method for preparing di-(N-methyl phthalimide) ether. The method comprises the following steps: firstly, one or two types of non-polar solvents and one kind of polar non-protonic solvent are mixed, the non-polar solvents are steamed out, then the mixed solvent reaches a certain proportion, N-methyl-4-nitryl phthalimide carries out self condensation reaction under the catalysis of one or two catalysts and normal pressure in the mixed solvent, heating and reflowing are conducted for 2 to 8 hours, and then the solvent is recovered, water is added, product is precipitatedafter cooling, and finally, tawny di-(N-methyl phthalimide) ether is obtained after filtering, washing and drying, the yield rate is 68 to 85 percent, and the melting point is 272.6 to 273 DEG C. The catalyst is organic acid salt and carbonate of organic acid salt of alkali metals and alkali-earth metals.
Description
Technical field
The present invention relates to a kind of organic preparation, the preparation method of particularly a kind of pair-(N-methyl phthalimide) ether.
Background technology
Two (N-methyl phthalimide) ether is a kind of meticulous organic products of high added value, is to synthesize 3,3 ', 4, the most important intermediate of 4 '-diphenyl ether tetraformic dianhydride (abbreviation ODPA-M).ODPA-M is one of important monomer of fire resistant resins such as new special engineering plastics polyimide, polyetherimide, polyester-imide, polyamide-imide, poly maleimide, polyaramide.It also can be used as the linking agent of synthesized polymer materials such as high performance heat resistant epoxy resin, urethane.ODPA-M type polyimide has outstanding mechanical property, electrical property, radiation resistance, can be in 180 ℃～230 ℃ scopes life-time service.Owing to be the flexible ehter bond that in the polyimide backbone structure, induced one, greatly reduce softening temperature, belong to thermoplastic polyimide, has good processing properties, aerospace and other high-tech sectors of being widely used in China, along with the increasingly mature of China's polyimide product development technology popularized, the specification kind is complete day by day, and ODPA-M will more and more come into one's own as emphasis novel material monomer.The expansion of Application Areas also can increase year by year to the demand and the output of two (N-methyl phthalimide) ether.So the further research to two (N-methyl phthalimide) ether technology of preparing has economic worth and social effect.
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.Other has the method for the composite catalyst that gas-phase silica, carbonate and phase-transfer catalyst mix, but in the polar aprotic solvent of big viscosity filtering catalyst, in industrial very difficult widespread use.Other has carry out two (N-methyl phthalimide) ethers of white condensation reaction preparation in the presence of binary organic catalyst Sodium Nitrite and Potassium monofluoride and ternary phase transfer catalyst Tetrabutyl amonium bromide, but this method is brought a large amount of inorganic salt in the water into, make that waste water is difficult to handle, cause the environmental protection cost to rise.
In sum, the preparation method of two (N-methyl phthalimide) ether also needs further to improve.
Summary of the invention
Defective or deficiency at above-mentioned prior art exists the objective of the invention is to, and the method for two (N-methyl phthalimide) ethers of a kind of preparation is provided, and this method production cost is low, environmental pollution is less, yield is high.
In order to realize above-mentioned task, the present invention takes following technical solution:
The method of two (N-methyl phthalimide) ethers of a kind of preparation, it is characterized in that, this method is at first mixed one or both apolar aprotic solvents with polar aprotic solvent, boil off apolar aprotic solvent then, makes mixed solvent reach certain ratio; Then with an amount of N-methyl-4-nitro phthalic imidine in above-mentioned mixed solvent, under the catalysis of one or both catalyzer, carry out self condensation reaction, reflux 2～8 hours, after reaction finishes, decompression and solvent recovery, add water, product, is after filtration separated out in cooling, after washing, the drying, obtain two (N-methyl phthalimide) ethers, wherein, described catalyzer is the organic acid salt of alkali-metal organic acid salt or alkaline-earth metal, catalyst levels be N-methyl-4-nitro phthalic imidine mole number 40%～300%.
Method production cost of the present invention is lower, the yield height, and quality is good.The yield of two (N-methyl phthalimide) ether products that employing present method obtains 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.And simple to operate, environmental pollution is little, carries out owing to be reflected under normal pressure and the backflow, and product yield improves, and solvent is easy to recovery of applied, has reduced three waste discharge.
Description of drawings
Fig. 1 is the relevant spectrogram of two (N-methyl phthalimide) ethers of preparing of the present invention: wherein, (a) being hydrogen nuclear magnetic resonance hydrogen collection of illustrative plates (1HNMR), (b) is nucleus magnetic resonance carbon collection of illustrative plates (13CNMR).
Below by embodiment the present invention is described in further detail.
Embodiment
According to technical scheme of the present invention, the method of two (the N monomethyl phthalic imidine) ethers of preparation, at first one or both apolar aprotic solvents are mixed with polar aprotic solvent, boil off apolar aprotic solvent then, make the mixed solvent that obtains reach certain ratio, then an amount of N-methyl-4-nitro phthalic imidine is being carried out self condensation reaction under the normal pressure under the catalyst in this mixed solvent, reflux 2～8 hours, the right solvent that reclaims, add water, product is separated out in cooling, after-filtration is through washing, obtain two (N-methyl phthalimide) ether products after the drying.Described catalyzer is the organic acid salt of alkali-metal organic acid salt or alkaline-earth metal, catalyst levels be N-methyl-4-nitro phthalic imidine mole number 40%～300%.
Above-mentioned apolar aprotic solvent is, wherein a kind of of normal hexane, hexanaphthene, normal heptane, octane, benzene,toluene,xylene, isopropyl ether, methyl tertiary butyl ether.
First-selected benzene of above-mentioned non-polar non-protic solvent and derivative thereof are as benzene,toluene,xylene.
Above-mentioned polar aprotic solvent is N, dinethylformamide, N,N-dimethylacetamide, wherein a kind of of propionic acid amide, N-Methyl pyrrolidone, HPT hexamethyl phosphoric triamine, methyl-sulphoxide.
The ratio of apolar aprotic solvent and polar aprotic solvent is 0%～10%.
Described catalyzer is sodium formiate, potassium formiate, wherein a kind of of lithium acetate, sodium acetate, potassium acetate, Quilonum Retard, yellow soda ash, salt of wormwood or two kinds.
Below be the embodiment that the contriver provides, need to prove, the invention is not restricted to these embodiment, these embodiment are only for further understanding the present invention, 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.
Embodiment 1:
In being housed, the 250ml there-necked flask of agitator, condenser, thermometer adds 10.3 gram (0.05mol) N-methyl-4-nitro phthalic imidines, 16.2 gram hexanaphthene and 70ml N, dinethylformamide, heated and stirred is to refluxing, constantly steam simultaneously hexanaphthene, by the time distillate liquid and be weighed as for 14 whens gram, add catalyzer: 3 gram (87%mol) sodium acetates and 3 gram (56%mol) yellow soda ash, refluxed 12 hours, reaction finishes, decompression and solvent recovery adds big water gaging, has a large amount of solids to separate out immediately.Filtrate is cooled to room temperature, separates out product, after filtration, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 5.78 grams, yield 68.6%, 268 ℃～270 ℃ of fusing points.
Embodiment 2:
In the 250ml there-necked flask of agitator, condenser, thermometer is housed, add catalyzer: 6 gram (60%mol) sodium acetates, 17.1 gram dimethylbenzene and 70ml dimethyl sulfoxide (DMSO), heated and stirred is to refluxing, constantly steam simultaneously dimethylbenzene, by the time recovered temperature reaches 138 when spending, and adds 10.3 gram (0.05mol) N-methyl-4-nitro phthalic imidines, refluxes 8 hours, reaction finishes, decompression and solvent recovery adds big water gaging, has a large amount of solids to separate out immediately.Filtrate is cooled to room temperature, separates out product, after filtration, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 6.27 grams, yield 74.6%, 268～270 ℃ of fusing points.
Embodiment 3:
In being housed, the 250ml there-necked flask of agitator, condenser, thermometer adds 10.3 gram (0.05mol) N-methyl-4-nitro phthalic imidines, 17.3 gram toluene and 70ml N-Methyl pyrrolidone, heated and stirred constantly steams hexanaphthene simultaneously to refluxing, when recovered temperature reaches 110-113 and spends by the time, add catalyzer: 12.0 gram (244%mol) Potassium ethanoates, refluxed 3 hours, reaction finishes, decompression and solvent recovery, add big water gaging, have a large amount of solids to separate out immediately.Filtrate is cooled to room temperature, separates out product, after filtration, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 6.88 grams, yield 81.9%, 268 ℃～270 ℃ of fusing points.
Embodiment 4:
In being housed, the 250ml there-necked flask of agitator, condenser, thermometer adds catalyzer: 3.6 gram (100%mol) Quilonum Retards (0.05mol), 15.0 gram benzene and 15.0 gram hexanaphthene and 85ml N, the N-N,N-DIMETHYLACETAMIDE, heated and stirred constantly steams benzene simultaneously to refluxing, when recovered temperature reaches 78-80 and spends by the time, add 10.3 gram N-methyl-4-nitro phthalic imidines, refluxed 6 hours, reaction finishes, decompression and solvent recovery, add big water gaging, have a large amount of solids to separate out immediately.Filtrate is cooled to room temperature, separates out product, after filtration, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 6.17 grams, yield 73.4%, 268 ℃～271 ℃ of fusing points.
Embodiment 5:
N-methyl-4-nitro the phthalic imidine that in the 250ml there-necked flask of agitator, condenser, thermometer is housed, adds 10.3 grams (0.05mol), 35 gram dimethylbenzene and 85ml N, the N-N,N-DIMETHYLACETAMIDE, heated and stirred is to refluxing, constantly steam simultaneously dimethylbenzene, by the time distillate liquid and be weighed as for 28 whens gram, add catalyzer: 6.9 gram (100%mol) salt of wormwood and 3.6 gram (100%mol) Quilonum Retards, refluxed 6 hours, reaction finishes, decompression and solvent recovery adds big water gaging, has a large amount of solids to separate out immediately.Filtrate is cooled to room temperature, separates out product, after filtration, after washing and the drying, obtain two (N-methyl phthalimide) ether products of the pale brown look of 6.72 grams, yield 80.0%, 268 ℃～270 ℃ of fusing points.
The relevant spectrogram of two (N-methyl phthalimide) ethers that the foregoing description obtains as shown in Figure 1.
Claims (5)
1. method for preparing two (N-methyl phthalimide) ethers, it is characterized in that, this method is at first mixed a kind of or two kinds of apolar aprotic solvents and polar aprotic solvent, boils off apolar aprotic solvent then, makes the mixed solvent that obtains reach certain ratio; Then an amount of N-methyl-4-nitro phthalic imidine is being carried out self condensation reaction under the normal pressure under the catalyst in above-mentioned mixed solvent, reflux 2～8 hours, reclaim solvent then, add water, product is separated out in cooling, after after filtration, washing, obtain two (N-methyl phthalimide) ethers after the drying; Wherein, described catalyzer is the organic acid salt of alkali-metal organic acid salt or alkaline-earth metal, catalyst levels be N-methyl-4-nitro phthalic imidine mole number 40%～300%.
2. the method for claim 1 is characterized in that, described apolar aprotic solvent is wherein a kind of of normal hexane, hexanaphthene, normal heptane, octane, benzene,toluene,xylene, isopropyl ether, methyl tertiary butyl ether.
3. the method for claim 1 is characterized in that, described apolar aprotic solvent is selected benzene, toluene or dimethylbenzene.
4. the method for claim 1 is characterized in that, described polar aprotic solvent is N, dinethylformamide, N,N-dimethylacetamide, propionic acid amide, N-Methyl pyrrolidone, HMPA, wherein a kind of of methyl-sulphoxide.
5. the method for claim 1 is characterized in that, described catalyzer is sodium formiate, potassium formiate, lithium acetate, sodium acetate, potassium acetate, wherein a kind of or two kinds mixture of Sodium Propionate, potassium propionate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100223988A CN101550102B (en) | 2009-05-07 | 2009-05-07 | Method for preparing di-(N-methyl phthalimide) ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100223988A CN101550102B (en) | 2009-05-07 | 2009-05-07 | Method for preparing di-(N-methyl phthalimide) ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101550102A CN101550102A (en) | 2009-10-07 |
| CN101550102B true CN101550102B (en) | 2010-12-01 |
Family
ID=41154626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100223988A Expired - Fee Related CN101550102B (en) | 2009-05-07 | 2009-05-07 | Method for preparing di-(N-methyl phthalimide) ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101550102B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896822A (en) * | 2014-03-31 | 2014-07-02 | 仪征市海帆化工有限公司 | Synthetic method of 3, 4'-oxo bisphthalimide |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110551085B (en) * | 2019-10-15 | 2021-10-26 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride |
| CN112724111B (en) * | 2020-12-30 | 2022-11-29 | 浙江清和新材料科技有限公司 | Method for preparing ODPA |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992406A (en) * | 1976-04-14 | 1976-11-16 | General Electric Company | Preparation of aromatic bisimides |
| CN1079734A (en) * | 1992-06-06 | 1993-12-22 | 上海市合成树脂研究所 | The method for preparing two-(N-methyl phthalimide) ether |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
| CN1958583A (en) * | 2006-11-21 | 2007-05-09 | 郁伟新 | Method for preparing double (N-methyl phthalimide) oxide |
| CN101007782A (en) * | 2007-01-26 | 2007-08-01 | 上海应用技术学院 | Bi(N-methylphthalic imidine) ester preparation method |
| CN101139315A (en) * | 2007-10-09 | 2008-03-12 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
-
2009
- 2009-05-07 CN CN2009100223988A patent/CN101550102B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992406A (en) * | 1976-04-14 | 1976-11-16 | General Electric Company | Preparation of aromatic bisimides |
| CN1079734A (en) * | 1992-06-06 | 1993-12-22 | 上海市合成树脂研究所 | The method for preparing two-(N-methyl phthalimide) ether |
| US6028203A (en) * | 1998-12-14 | 2000-02-22 | General Electric Company | Phase transfer catalyzed method for prepared oxybisphthalic compounds |
| CN1958583A (en) * | 2006-11-21 | 2007-05-09 | 郁伟新 | Method for preparing double (N-methyl phthalimide) oxide |
| CN101007782A (en) * | 2007-01-26 | 2007-08-01 | 上海应用技术学院 | Bi(N-methylphthalic imidine) ester preparation method |
| CN101139315A (en) * | 2007-10-09 | 2008-03-12 | 上海市合成树脂研究所 | Method for preparing di(N-methyl phthalimide) ether |
Non-Patent Citations (6)
| Title |
|---|
| Zhiqiang Zhang et al.Investigation on the New Synthetic Reactions and Mechanisms of Substituted Diphenyl Ethers.《Chinese Chemical Letters》.1991,第2卷(第9期),第687-688页. * |
| Zhiqiang Zhang et al.Nucleophilic Aromatic Substitution of Nitrobenzenes with Nitrite Ion.《Chinese Chemical Letters》.1997,第8卷(第3期),第193-194页. * |
| 张志强 等.二苯醚系高分子单体的新合成路线.《化学通报》.1996,(第5期),第27-29页. |
| 张志强等.二苯醚系高分子单体的新合成路线.《化学通报》.1996,(第5期),第27-29页. * |
| 田正华 等.取代二苯醚的新合成反应研究.《化学通报》.1989,(第7期),第36-39页. |
| 田正华等.取代二苯醚的新合成反应研究.《化学通报》.1989,(第7期),第36-39页. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896822A (en) * | 2014-03-31 | 2014-07-02 | 仪征市海帆化工有限公司 | Synthetic method of 3, 4'-oxo bisphthalimide |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101550102A (en) | 2009-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101550102B (en) | Method for preparing di-(N-methyl phthalimide) ether | |
| CN101880363B (en) | Allylation hyperbranched polyphenyl ether modified bismaleimide resin and preparation method thereof | |
| WO2023010800A1 (en) | Remodelable and degradable biomass benzoxazine resin and preparation method therefor | |
| CN103435504B (en) | A kind of preparation method of degradable primary amine curing agent | |
| CN108456303B (en) | Bio-based polyarylether resin containing furan ring structure and preparation method thereof | |
| CN104177579B (en) | The preparation method of a kind of benzoxazine compounds | |
| CN116768710A (en) | Process for preparing biphenol | |
| CN100460390C (en) | Bi(N-methylphthalic imidine) ester preparation method | |
| CN101381307B (en) | 4-ethyl benzoate phenyl p-dihydroxy benzene and preparation method and application thereof | |
| WO2019148502A1 (en) | Bio-based polyarylene ether resin containing furan ring structure and preparation method therefor | |
| CN112574148B (en) | Preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) | |
| CN106905529A (en) | Cyano-containing and fluorenyl bimaleimide resin and preparation method thereof | |
| CN101121644B (en) | Method for preparing 4,4'-dihydroxydiphenyl ether | |
| CN1958583A (en) | Method for preparing double (N-methyl phthalimide) oxide | |
| CN115583929B (en) | Preparation method of bisphenol A diether dianhydride | |
| CN101220146A (en) | Naphthalene nucleus modified polyarylether containing fluorene and synthesizing method thereof | |
| CN101016261B (en) | Preparing method of 4-phthalimidephenol | |
| CN101560166B (en) | Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene | |
| CN116162241A (en) | Polyimide resin containing tetraphenyl naphthalene unit and preparation method thereof | |
| CN114656640A (en) | Phenolphthalein type co-sulfate and preparation method thereof | |
| CN111807964A (en) | Preparation method of 4,4 '-dinitro-2, 2' -bistrifluoromethyldiphenyl ether | |
| CN101100446A (en) | Preparation method for 2,2-di[3-amino-4-(4-cyanophenoxy)phenyl]propane | |
| CN115286600A (en) | Preparation method of bisphenol A diether dianhydride | |
| CN116730803A (en) | Preparation method of biphenol | |
| CN101195580A (en) | Process for producing 2,2-dual [3-amido-4-(4-nitrophenoxy) phenyl] propane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101201 Termination date: 20110507 |