CN100503569C - Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane - Google Patents
Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane Download PDFInfo
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- CN100503569C CN100503569C CNB200710040578XA CN200710040578A CN100503569C CN 100503569 C CN100503569 C CN 100503569C CN B200710040578X A CNB200710040578X A CN B200710040578XA CN 200710040578 A CN200710040578 A CN 200710040578A CN 100503569 C CN100503569 C CN 100503569C
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- diphenyl methane
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Abstract
This invention relates to a method for preparing 4,4'-bis(4-carboxyphthaleinimido)-3,3'-dimethyl diphenylmethane. The method comprises: dissolving 4,4'-diamino-3,3'-dimethyl diphenylmethane and trimellitic anhydride at a mol. ratio of 1.00:(1.98-2.02) into a highly polar aprotic organic solvent, stirring for reaction at room temperature to obtain a homogeneous solution, adding azeotropic dehydrator, performing azeotropic dehydration for 2-12 h, recovering the azeotropic dehydrator and part of the highly polar aprotic organic solvent, cooling to room temperature, adding water, precipitating the product, filtering, washing, and vacuum-drying. The method has such advantages as easy operation, little pollution, high yield, high purity (above 99%), and recoverable solvent, and is suitable for industrialization.
Description
Technical field
The invention belongs to the preparation field of organic compound, particularly relate to a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane.
Background technology
4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM) is one of important raw and processed materials of preparation polyamide-imide resin, polyesterimide resin, simultaneously, also is the good heat-proof modifier or the solidifying agent of Resins, epoxy.
Relevant 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), not seeing as yet so far has patent or disclosed bibliographical information.
Summary of the invention
4,4 '-two (4-carboxyl phthalimide groups)-3 of the present invention, 3 '-dimethyl diphenyl methane chemical equation is as follows:
The invention provides a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane,
This method technology is simple, cost is low, environmentally friendly, yield is high, purity reaches more than 99%, is fit to suitability for industrialized production.
A kind of 4,4 '-two (4-carboxyl phthalimide groups)-3 of the present invention, the preparation method of 3 '-dimethyl diphenyl methane comprises the steps:
(1) mol ratio is 4 of 1.00:1.98～2.02,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and trimellitic anhydride (TMA), in strong polar non-proton organic solvent, stirring reaction under room temperature is behind the one-tenth homogeneous phase solution, add azeotropy dehydrant, heat temperature raising refluxes, and 85 ℃ ~ 180 ℃, azeotropic dehydration reaction 2～12 hours;
(2) reclaim the strong polar non-proton organic solvent of azeotropy dehydrant and part, the cooling reaction solution adds water to room temperature, separates out product, filtration, washing, and vacuum-drying obtains 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane.
Described strong polar non-proton organic solvent is N, one or more mixtures in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), the dimethyl sulfoxide (DMSO) (DMSO).
Described trimellitic anhydride (TMA) is 10～30:20～200 (grams per milliliters) with the weightmeasurement ratio of strong polar non-proton organic solvent.
The described azeotropy dehydrant of step (1) is one or more mixtures in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene.
The volume ratio of described strong polar non-proton organic solvent of step (1) and azeotropy dehydrant is 1.0:0.1～10.
Beneficial effect of the present invention is as follows:
(1) the present invention is preparation 4,4 '-two (4-carboxyl phthalimide groups)-3, the commercial run of 3 '-dimethyl diphenyl methane;
(2) environmentally friendly, the three wastes are few;
(3) simple to operate, reaction process is carried out under normal pressure, does not relate to also not producing corrosives, equipment is not had particular requirement, and less investment can be finished preparation 4 in same reactor, 4 '-two (4-carboxyl phthalimide groups)-3, the operating process of 3 '-dimethyl diphenyl methane;
(4) product yield and purity are all very high;
(5) solvent is recyclable applies mechanically repeatedly, and this not only can reduce production costs, and has stopped environmental pollution effectively;
(6) production cost of products is cheap, helps it and further applies.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 11.3 gram (0.05 moles) 4,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) add in the reactor together, under the room temperature stirring and dissolving evenly after, add 19.2 gram (0.1 mole) trimellitic anhydride (TMA), after stirring reaction is homogeneous phase, add 60 milliliters of dimethylbenzene, stir, heat temperature raising refluxes, after the azeotropic dehydration imidization 8 hours, reclaim the strong polar non-proton organic solvent N-N-methyl-2-2-pyrrolidone N-(NMP) of azeotropy dehydrant dimethylbenzene and part, close heating system, stir, naturally cool to room temperature, add water, separate out white solid product, filter, with an amount of cold nmp solvent drip washing 2 times, vacuum-drying, obtain 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM), purity 99.3%, according to 4,4 '-diamino-3,4,4 ' of the charging capacity of 3 '-dimethyl diphenyl methane (MDT) and acquisition-two (4-carboxyl phthalimide group)-3, the amount of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), recording yield is 96%.
Embodiment 2
With 11.3 gram (0.05 moles) 4,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and 80 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc) adds in the reactor together, under the room temperature stirring and dissolving evenly after, add 19.2 gram (0.1 mole) trimellitic anhydride (TMA), after stirring reaction is homogeneous phase, add 80 milliliters of toluene, stir, heat temperature raising refluxes, and the azeotropic dehydration imidization was reclaimed the strong polar non-proton organic solvent N of azeotropy dehydrant toluene and part after 12 hours, N-N,N-DIMETHYLACETAMIDE (DMAc), close heating system, stir, naturally cool to room temperature, add water, separate out white solid product, filter, with an amount of cold N, N-N,N-DIMETHYLACETAMIDE (DMAc) eluent solvent 2 times, vacuum-drying obtains 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM), purity 99.1%, according to 4,4 '-diamino-3,4 of the charging capacity of 3 '-dimethyl diphenyl methane (MDT) and acquisition, 4 '-two (4-carboxyl phthalimide groups)-3, the amount of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), recording yield is 92%.
Embodiment 3
With 11.3 gram (0.05 moles) 4,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) add in the reactor together, under the room temperature stirring and dissolving evenly after, add 19.2 gram (0.1 mole) trimellitic anhydride (TMA), after stirring reaction is homogeneous phase, add 60 milliliters of dimethylbenzene, stir, heat temperature raising refluxes, after the azeotropic dehydration imidization 2 hours, reclaim the strong polar non-proton organic solvent N-N-methyl-2-2-pyrrolidone N-(NMP) of azeotropy dehydrant dimethylbenzene and part, close heating system, stir, naturally cool to room temperature, add water, separate out white solid product, filter, with an amount of cold nmp solvent drip washing 2 times, vacuum-drying, obtain 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM), purity 95.2%, according to 4,4 '-diamino-3,4,4 ' of the charging capacity of 3 '-dimethyl diphenyl methane (MDT) and acquisition-two (4-carboxyl phthalimide group)-3, the amount of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), recording yield is 98%.
Embodiment 4
With 11.3 gram (0.05 moles) 4,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and 80 milliliters of N, dinethylformamide (DMF) adds in the reactor together, under the room temperature stirring and dissolving evenly after, add 19.4 gram (0.101 mole) trimellitic anhydride (TMA), after stirring reaction is homogeneous phase, add 100 milliliters of toluene, stir, heat temperature raising refluxes, and the azeotropic dehydration imidization was reclaimed the strong polar non-proton organic solvent N of azeotropy dehydrant toluene and part after 12 hours, dinethylformamide (DMF), close heating system, stir, naturally cool to room temperature, add water, separate out white solid product, filter, with an amount of cold N, dinethylformamide (DMF) eluent solvent 2 times, vacuum-drying obtains 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM), purity 98.1%, according to 4,4 '-diamino-3,4 of the charging capacity of 3 '-dimethyl diphenyl methane (MDT) and acquisition, 4 '-two (4-carboxyl phthalimide groups)-3, the amount of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), recording yield is 93%.
Embodiment 5
With 11.3 gram (0.05 moles) 4,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and 100 milliliters of N, dinethylformamide (DMF) adds in the reactor together, under the room temperature stirring and dissolving evenly after, add 19.0 gram (0.099 mole) trimellitic anhydride (TMA), after stirring reaction is homogeneous phase, add 100 milliliters of toluene, stir, heat temperature raising refluxes, after the azeotropic dehydration imidization 12 hours, reclaim the strong polar non-proton organic solvent N of azeotropy dehydrant toluene and part, dinethylformamide (DMF) is closed heating system, stir, naturally cool to room temperature, add water, separate out white solid product, filter, with an amount of cold N, dinethylformamide (DMF) eluent solvent 2 times, vacuum-drying, obtain 4,4 '-two (4-carboxyl phthalimide groups)-3,3 '-dimethyl diphenyl methane (BTMI-DMDPM), purity 99.1%, according to 4 of the charging capacity of trimellitic anhydride (TMA) and acquisition, 4 '-two (4-carboxyl phthalimide groups)-3, the amount of 3 '-dimethyl diphenyl methane (BTMI-DMDPM), recording yield is 95%.
Claims (6)
1. one kind 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane comprises the steps:
(1) mol ratio is 4 of 1.00:1.98～2.02,4 '-diamino-3,3 '-dimethyl diphenyl methane (MDT) and trimellitic anhydride (TMA), in strong polar non-proton organic solvent, stirring reaction under room temperature is behind the one-tenth homogeneous phase solution, add azeotropy dehydrant, heat temperature raising refluxes, and 85 ℃ ~ 180 ℃, azeotropic dehydration reaction 2～12 hours;
(2) reclaim the strong polar non-proton organic solvent of azeotropy dehydrant and part, the cooling reaction solution adds water to room temperature, separates out product, filters and use solvent wash, vacuum-drying.
2. according to claim 1 a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane, it is characterized in that, described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), the dimethyl sulfoxide (DMSO) (DMSO).
3. according to claim 1 a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane, it is characterized in that described trimellitic anhydride (TMA) is 10 grams～30 grams with the weightmeasurement ratio of strong polar non-proton organic solvent: 20 milliliters～200 milliliters.
4. according to claim 1 a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane is characterized in that, the described azeotropy dehydrant of step (1) is selected from one or more mixtures in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene.
5. according to claim 1 a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane is characterized in that, the volume ratio of described strong polar non-proton organic solvent of step (1) and azeotropy dehydrant is 1.0:0.1～10.
6. according to claim 1 a kind of 4,4 '-two (4-carboxyl phthalimide groups)-3, the preparation method of 3 '-dimethyl diphenyl methane, it is characterized in that, the described cleaning solvent of step (2) is N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) or N-N-methyl-2-2-pyrrolidone N-(NMP).
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| CNB200710040578XA CN100503569C (en) | 2007-05-11 | 2007-05-11 | Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane |
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| CNB200710040578XA CN100503569C (en) | 2007-05-11 | 2007-05-11 | Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane |
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| CN100503569C true CN100503569C (en) | 2009-06-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101230031B (en) * | 2008-02-18 | 2010-06-02 | 东华大学 | Method for preparing 2,2-bi[3-(4-carboxylphthalimide)-4-hydroxyphenyl] hexafluoropropane |
| CN101941933B (en) * | 2010-09-20 | 2012-09-05 | 东华大学 | 2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene and preparation method thereof |
| CN101921222B (en) * | 2010-09-20 | 2012-09-05 | 东华大学 | 3,3',5,5'-tetramethyl-4,4'-di(4-maleimide-2-trifluoromethylphenoxy) biphenyl and preparation method thereof |
| CN101941934B (en) * | 2010-09-20 | 2012-09-05 | 东华大学 | 4,4'-bi-(4-maleimide-2-trifluoromethanephenoxy)biphenyl and preparation method thereof |
| CN101921221B (en) * | 2010-09-20 | 2012-09-05 | 东华大学 | 2-tertiarybutyl-1,4-bis(2-trifluoromethyl-4-maleimide phenoxyl) benzene and preparation method thereof |
| CN101955458B (en) * | 2010-09-20 | 2012-09-05 | 东华大学 | 2,2-di [4-(2-trifluoromethyl-4-maleimide phenyloxy) phenyl] propane and preparation method thereof |
| CN110698644A (en) * | 2019-10-08 | 2020-01-17 | 东华大学 | Phthalimide glycidyl ester epoxy resin and preparation method thereof |
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