CN102363607B - Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium - Google Patents
Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium Download PDFInfo
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- CN102363607B CN102363607B CN 201110385605 CN201110385605A CN102363607B CN 102363607 B CN102363607 B CN 102363607B CN 201110385605 CN201110385605 CN 201110385605 CN 201110385605 A CN201110385605 A CN 201110385605A CN 102363607 B CN102363607 B CN 102363607B
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- MWTPWZNBIZUXBT-UHFFFAOYSA-O C[n]1c[n+](CCCCS(O)(=O)=O)cc1 Chemical compound C[n]1c[n+](CCCCS(O)(=O)=O)cc1 MWTPWZNBIZUXBT-UHFFFAOYSA-O 0.000 description 1
- CHVFGCXPLGAAQN-UHFFFAOYSA-O OS(CCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1)(=O)=O Chemical compound OS(CCC[P+](c1ccccc1)(c1ccccc1)c1ccccc1)(=O)=O CHVFGCXPLGAAQN-UHFFFAOYSA-O 0.000 description 1
Abstract
The invention relates to a method for synthesizing a monomaleimide or bismaleimide derivative. In the method, monomaleamic acid or bimaleamic acid is used as a raw material, and a cyclization reaction is performed in the strongly acidic room-temperature ionic liquid medium, and a target product of which the yield is over 80 percent can be obtained. Unlike the conventional synthesis method, the synthesis route avoids using an acetic anhydride dehydrating agent and a strongly corrosive mineral acid catalyst. After reaction, the reaction mixture is extracted by an organic solvent, and the high-purity target product can be obtained by simple separation. The step of washing the product with a large volume of water for removing the catalyst and dehydrating agent in the conventional process is avoided. Because the catalyst provided by the invention can be used repeatedly and the synthesis method avoids discharging waste water, water gas and waste residue, the method can be used to synthesize the monomaleimide or bismaleimide derivative in a green, environment-friendly and low-cost way.
Description
Technical field
The present invention relates to the preparation method of list or bismaleimides, utilize the strongly-acid ionic liquid at room temperature to be reaction medium, make list or span come the amido acid cyclisation and obtain target product.Catalyzer proposed by the invention is repeatedly reusable, and the reaction process three-waste free discharge is a green, environmental protection and synthetic route cheaply.
Background technology
List or bismaleimides are the important fine chemical products of a class, have widely purposes.Wherein, single maleimide be mainly used in natural rubber and elastomeric vulcanizing agent, thermoplastic resin modified dose.Resin after its modification has good thermotolerance and processibility, has been widely used in the macromolecular materials such as ABS, polypropylene, PVC, PMMA.In addition, single maleimide also has good anti-microbial activity, as the marine equipment stain control agent, be applied in the equipment such as steamer, warship, sewer line, can prevent that effectively harmful organism breeds at equipment in the sealing, then nontoxic to other biological, do not pollute the marine site.But autohemagglutination when bismaleimides heats because of it, can't emit the small molecules volatile matter, polymerisate has higher heat resisting temperature and electrical insulation capability preferably, as fibre composite matrix resin, packaged material etc., has been widely used in the industries such as aerospace and electronic apparatus.
Yet, loaded down with trivial details synthesis technique and the expensive reaction reagent of use, cause the price of single (two) maleimide high (6.8 ten thousand yuan/tons of the average prices of the single maleimide in area, East China in 2011), increase user's use cost, also limited the widely application of these materials.Therefore, the developing low-cost synthesis technique is single (two) maleimide production and the department of application problem demanding prompt solution.
Usually, single (two) maleimide obtains through two-step reaction.That is, at first maleic anhydride and organic amine reaction are generated single (two) maleinamic acid, again the latter is generated product through dehydration closed-loop.A rear step is the key of synthetic single (two) maleimide.In most cases, it is catalyzer that metal-salt or organic amine are adopted in reaction, take acetic anhydride as dewatering agent, uses polar organic solvent such as acetone and dimethyl formamide (DMF) etc.Relevant building-up process has a detailed description in US Patent No. 3127414 and US4193747, Japanese Patent JP9268174.Owing in the post-reaction treatment process, must remove the dewatering agent diacetyl oxide for water, can cause the generation of a large amount of acid-bearing wastewaters, cause huge environmental stress.Importantly, diacetyl oxide is as easy toxogen material processed, and various countries have all formulated strict buying and used regulation, cause it expensive, transportation, use and manage all and be very limited, this also is to cause the high major cause of single (two) maleimide price.In order to overcome these defectives, existing extensive work research does not use diacetyl oxide to be the technique of dewatering agent.Be typically azeotropic dehydration closed loop method.Adopting toluene such as Japanese Patent JP5368770 is azeotropic aqua, in the presence of mineral acid (phosphoric acid, the vitriol oil, tosic acid, Vanadium Pentoxide in FLAKES etc.) catalyzer, has obtained the target product of high yield.US Patent No. 4705866 has reported also that with the organic tin compound as catalyzer, ethyl acetate, toluene etc. is the method for azeotropic aqua.Although these techniques have been avoided the use diacetyl oxide, yet the last handling process of product is removed catalyzer because of needs and is become loaded down with trivial details, and can produce a large amount of waste water inevitably.
Ionic liquid at room temperature is the focus of Recent study, be called as green synthetic agent (referring to, Amanda C.Cole etc., J.Am.Chem.Soc.2002,124,5962-5963), and be applied at industrial sector.In the ionic liquid at room temperature, strong Bu Laosite acidic ion liquid enjoys the investigator to favor.Because it at room temperature is flow state, non-volatile, particularly it does not dissolve each other with most organic solvent, for the aftertreatment of reacting provides greatly convenience, can be used for many organic reactions.Typical example is its catalytic esterification.Common esterification is carried out under the acid catalysis of ore deposit, and reaction needs the finishing sequences such as neutralization, washing after finishing.And when using ionic liquid, only need reaction product is simply separated with ionic liquid, just can obtain product, ionic liquid can be repeatedly used simultaneously, can greatly save production cost the minimizing environmental stress.
Based on the characteristics of ionic liquid and the present situation of above-mentioned list (two) maleimide synthesis technique, particularly so far without the report that utilizes ionic liquid for the synthetic maleimide of medium, it is medium that the present invention proposes to adopt the strongly-acid ionic liquid at room temperature, makes single (two) maleinamic acid cyclisation generate the synthesis technique of target product.The present invention has not only got rid of the dewatering agent aceticanhydride that uses in the prior synthesizing method.After the reaction, reaction mixture by simple separation, just can obtain highly purified target product through organic solvent extraction, has avoided in the traditional technology, makes in a large number to wash product with water to remove the operation of catalyzer.Because catalyzer proposed by the invention can be repeatedly, and this synthetic method three-waste free discharge, therefore adopts the present invention, can green, environmental protection synthesize list or bismaleimide sulfonamide derivatives, and will greatly reduce the cost of product.
Summary of the invention
The novel method that the present invention aims to provide a kind of green, environmental protection and synthesizes at low cost list or bismaleimide sulfonamide derivatives.
List of the present invention or bismaleimides prepare by following method:
In acid ionic liquid at room temperature, add list or span and come amido acid, stir lower reacting by heating after a few hours, add organic solvent, the reaction mixture that will be divided into two-phase separates, and namely gets target product after organic solvent is removed in the organic phase distillation.
Single maleinamic acid of the present invention has following chemical structure:
Wherein, R
1Be H, OH, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, allyl group and aryl.When R1 was aryl, it had following structure:
In the formula, R is H, OH, F, Cl, Br, I ,-COOH ,-CHO ,-CN, trifluoromethyl, ethanoyl, nitro, allyloxy, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, allyl group, vinyl.
Span of the present invention comes amido acid to have following chemical structure:
Wherein,
In the following formula, n=1-6.
Above-mentioned list or span come amido acid to prepare by the following method: in acetone, maleic anhydride and organic amine are mixed, behind the stoichiometric number hour, reaction mixture after filtration, organic solvent washing, drying can obtain product.Preferred reaction conditions is, 0 ℃ of temperature of reaction is to room temperature.
According to technique of the present invention, the structure of single maleimide derivatives of acquisition is:
In the formula, R
1Chemical structure identical with aforementioned R1.
According to technique of the present invention, the structure of the bismaleimide sulfonamide derivatives of acquisition is:
In the formula, R
2Chemical structure and aforementioned R
2Identical.
Acid ionic liquid at room temperature of the present invention has following chemical structure:
In the formula, Z and R
3Be the alkyl of C1～C6, m=1,2, X are sulfuric acid, nitric acid, phosphoric acid, acetic acid, tosic acid, trifluoroacetic acid, trifluoromethanesulfonic acid.
Synthesizing of above-mentioned ionic liquid, and the method for reference literature report (Amanda C.Cole etc., J.Am.Chem.Soc.2002,124,5962-5963).
The present invention adopts the organic solvent extracting access method to the separation of product.Used organic solvent is acetone, butanone, pimelinketone, ether, tetrahydrofuran (THF), DMF, DMAC, DMSO, NMP, tetramethylene sulfone, methyl alcohol, ethanol, propyl carbinol, toluene, dimethylbenzene, ethyl acetate, hexanaphthene.
Temperature of reaction of the present invention is 40 ℃-160 ℃, and preferable reaction temperature is 80 ℃.
Reaction times of the present invention is 2-8 hour, preferred 5-6 hour.
The weight ratio of reaction raw materials of the present invention and ionic liquid is 1.0: 0.5～1.0: 20.0.Preferred 1.0: 10.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Synthesizing of embodiment 1 N-aryl maleinamic acid
Place 200 milliliters of acetone in 500 milliliters of reaction flasks, stir the lower 98 gram maleic anhydrides (1.0 moles) that add, after stirring, slowly drip 93 gram aniline, the reaction mixture vigorous stirring is after 5 hours, and formed yellow mercury oxide filters, is drying to obtain product.
Similarly, adopt present embodiment, can come amido acid, N-(4-carboxyl phenyl) maleinamic acid by the synthesizing diphenyl methane span
N-(4-trifluoromethyl) maleinamic acid and N-(4-hydroxy phenyl) maleinamic acid.
Synthesizing of embodiment 2 imidazole type sulfuric acid chamber temperature ionic liquids
The molecular structure of the described imidazole type sulfuric acid chamber of present embodiment geothermal liquid is as follows:
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002, the method for 124,5962-5963 report is synthetic.Add 40 gram N-Methylimidazoles and 68 gram Isosorbide-5-Nitrae-butane group sultone in reaction flask, stirring reaction gets white solid.Add the vitriol oil 9.8 grams behind the purifying, stirring reaction 6 hours obtains colourless liquid, namely gets object ion liquid after the ether washing.
1HNMR(300MHz，D
2O)δ8.52(s，1H)，7.25(d，J＝17.4Hz，2H)，4.03(t，J＝7.0Hz，2H)，3.67(s，3H)，2.81-2.64(m，2H)，1.79(dd，J＝15.0，7.4Hz，2H)，1.53(dd，J＝15.5，8.0Hz，2H).
Synthesizing of embodiment 3 triphenylphosphine type sulfuric acid chamber temperature ionic liquids
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002, the method for 124,5962-5963 report is synthetic.Add triphenylphosphine and 1, the 3-propyl sultone of equimolar amount in reaction flask, add toluene again, stirring also refluxes and spends the night, and gets white solid.The vitriol oil that adds equimolar amount behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, namely get object ion liquid after the ether washing.
Synthesizing of embodiment 4 pyrrolidone type sulfuric acid chamber temperature ionic liquids
The molecular structure of the described imidazole type sulfuric acid chamber of present embodiment geothermal liquid is as follows:
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002, the method for 124,5962-5963 report is synthetic.Add pyrrolidone and 1, the 3-propyl sultone of equimolar amount in reaction flask, add toluene again, stirring also refluxes and spends the night, and gets white solid.The vitriol oil that adds equimolar amount behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, namely get object ion liquid after the ether washing.
Synthesizing of embodiment 5 imidazole type tosic acid ionic liquid at room temperature
The molecular structure of the described imidazole type sulfuric acid chamber of present embodiment geothermal liquid is as follows:
With reference to Amanda C.Cole etc., J.Am.Chem.Soc.2002, the method for 124,5962-5963 report is synthetic.Add equimolar N-Methylimidazole and Isosorbide-5-Nitrae-butane group sultone in reaction flask, stirring reaction gets white solid.Add equimolar tosic acid behind the purifying, 70 ℃ of stirring reactions 6 hours obtain colourless liquid, namely get object ion liquid after the ether washing.
Synthesizing of embodiment 6 N-phenylmaleimides
Add the N-phenyl maleimide acid (19 gram) of being synthesized by embodiment 1 and the imidazole type sulfuric acid chamber temperature ionic liquid (190 gram) that is synthesized by embodiment 2 in 500 milliliters of reaction flasks, be warming up to 60 ℃, stirring reaction 5 hours, after reaction finishes, in reaction system, add ether, after stirring evenly, isolate supernatant liquid, desolventizing is drying to obtain product.
Synthesizing of embodiment 7 N-(4-carboxyl phenyl) maleimide
Add 24 gram N-(4-carboxyl phenyl) maleinamic acids in 500 milliliters of reaction flasks, the triphenylphosphine type sulfuric acid chamber geothermal liquid ionic liquid that 240 grams are synthesized by embodiment 3, heat up 60 ℃, reacted 5 hours, reaction adds ether after finishing in reaction system, isolate supernatant liquid, desolventizing obtains faint yellow solid.
1H?NMR(300MHz，DMSO)δ8.05(d，J＝8.7Hz，2H)，7.50(d，J＝8.6Hz，2H)，7.23(s，2H)。
Synthesizing of embodiment 8 N-(4-trifluoromethyl) maleimide
Add 26 gram N-(4-trifluoromethyl) maleinamic acids in 500 milliliters of reaction flasks, the pyrrolidone type sulfuric acid chamber temperature ionic liquid that 260 grams are synthesized by embodiment 4, heat up 60 ℃, reacted 7 hours, reaction adds ether after finishing in reaction system, isolate supernatant liquid, desolventizing obtains white solid.
19F?NMR(300MHz，CDCl
3)δ-63；
1H?NMR(300MHz，CDCl
3)δ6.56(2H)，7.1(2H)，7.5(2H)。
Synthesizing of embodiment 9 N-(4-hydroxy phenyl) maleimide
Add 21 gram N-(4-hydroxy phenyl) maleinamic acids in 500 milliliters of reaction flasks, the imidazole type sulfuric acid chamber temperature ionic liquid that 210 grams are synthesized by embodiment 2, heat up 60 ℃, reacted 7 hours, reaction adds ether after finishing in reaction system, isolate supernatant liquid, desolventizing obtains light yellow needle-like crystal.
Synthesizing of embodiment 10 diphenyl methane dimaleimides
Add 39 gram ditane spans in 500 milliliters of reaction flasks and come amido acid, the imidazole type tosic acid ionic liquid at room temperature that 390 grams are synthesized by embodiment 5, heat up 80 ℃, reacted 9 hours, after reaction finishes, add dimethyl formamide in reaction system, isolate supernatant liquid, desolventizing obtains faint yellow solid.Thin layer chromatography analysis and commercially available product indifference.
Claims (5)
1. the method for a synthetic list or bismaleimide sulfonamide derivatives, it is characterized in that in temperature of reaction be 40-160 ℃, come amido acid as raw material take list or span, in acid Room Temperature Ionic Liquid, react and made list or span come the amido acid cyclisation to form list or bismaleimide sulfonamide derivatives in 2-8 hour:
The weight ratio of described reaction raw materials and ionic liquid is 1.0: 0.5～1.0: 20.0;
Described single maleinamic acid has following chemical structure:
Described span comes amido acid to have following chemical structure:
The structure of described single maleimide derivatives is:
The structure of described bismaleimide sulfonamide derivatives is:
Described strongly-acid ionic liquid at room temperature has following chemical structure:
Wherein, R
1Be H, OH, CH
2COOH, CH
2CH
2COOH, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, allyl group or aryl; Described aryl has following structure:
In the formula, R be H, OH ,-CHO, F, Cl, Br, I ,-CHO ,-COOH ,-CN, trifluoromethyl, ethanoyl, nitro, allyloxy, C
1～C
6Alkyl, cyclopentyl, cyclohexyl, allyl group or vinyl;
Z and R
3Be the alkyl of C1～C6;
n＝1-6；
M=1 or 2;
X is sulfuric acid, nitric acid, phosphoric acid, acetic acid, tosic acid, trifluoroacetic acid or trifluoromethanesulfonic acid.
2. described method according to claim 1 is characterized in that, after reaction finished, reaction product was through the organic solvent extraction purifying; Described organic solvent is acetone, butanone, pimelinketone, ether, tetrahydrofuran (THF), N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, tetramethylene sulfone, methyl alcohol, ethanol, propyl carbinol, toluene, dimethylbenzene, ethyl acetate or hexanaphthene.
3. described method according to claim 1 is characterized in that described temperature of reaction is 80 ℃.
4. described method according to claim 1 is characterized in that the described reaction times is 5-6 hour.
5. described method according to claim 1, the weight ratio that it is characterized in that described reaction raw materials and ionic liquid is 1.0: 10.
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| CN105017127A (en) * | 2015-07-08 | 2015-11-04 | 聊城大学 | Preparation method for N,N'-4,4'-diphenylmethyene bismaleimide |
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