CN101948419A - Method for preparing methyl bismaleimide - Google Patents
Method for preparing methyl bismaleimide Download PDFInfo
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- CN101948419A CN101948419A CN 201010276983 CN201010276983A CN101948419A CN 101948419 A CN101948419 A CN 101948419A CN 201010276983 CN201010276983 CN 201010276983 CN 201010276983 A CN201010276983 A CN 201010276983A CN 101948419 A CN101948419 A CN 101948419A
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- methyl
- triethylamine
- bismaleimides
- acetone
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Abstract
The invention provides a method for preparing methyl bismaleimide. The methyl bismaleimide in the method comprises the following raw materials apart from water and acetone solvent in part by weight: 10 to 15 parts of 2,4-diaminotoluene, 18 to 25 parts of maleic anhydride, 20 to 35 parts of acetic anhydride serving as a dehydrating agent, 3 to 6 parts of triethylamine serving as a catalyst and 0.18 to 0.5 part of magnesium acetate serving as another catalyst, wherein the amount of used acetone solvent is 100 to 200ml. The preparation method comprises the following steps of: (1) reacting the 2,4-diaminotoluene with the maleic anhydride in the acetone solvent at the normal temperature and normal pressure for 0.5 to 1.5 hours; (2) raising the temperature to 62 to 68 DEG C and performing refluxing dehydration for 2 to 3 hours under the combined action of azeotrope, the acetic anhydride serving as the dehydrating agent, and the triethylamine and the magnesium acetate serving as acid catalysts; (3) cooling the obtained product to 6 to 9 DEG C by adding ice water, settling out the product for 40 minutes by adding water, separating out crystals and filtering, washing the crystals until the pH value is neutral, and drying to obtain the methyl bismaleimide finished product; and (4) performing reduced pressure distillation on filtered and washed mother liquor, and recovering the acetone, the triethylamine and the acetic anhydride from the mother liquor for recycling.
Description
Technical field
The present invention relates to chemical industry resin field, specially refer to the preparation method of methyl bismaleimides.
Background technology
Bismaleimides is the insulating material that preparation is used for space flight, aviation and part weaponry, and it is high-abrasive material, functional composite material that space flight, aeronautic structure material all require, polyimide resin etc.Bismaleimides is again the important raw and processed materials of agrochemicals and synthetic drugs, also can be used as the heat-proof modifier of macromolecular material (as PP, ABS, nylon etc.) Resins, epoxy and is used as common monomer that other resin of modification uses etc.The bismaleimide resin matrix composite is widely used in aerospace field, is the important materials of defense advanced weapon system.But the diphenyl methane dimaleimide resin of universal non-modified has defectives such as crisp hard, the poor toughness of quality, resistance to cracking and shock resistance difference.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of high tenacity, the high temperature resistant and methyl bismaleimides that shock resistance is good.
For achieving the above object, concrete technical scheme of the present invention is:
The methyl bismaleimides dewater and acetone solvent outside, the weight part component of its raw material is as follows:
2,4 diaminotoluene 10-15
MALEIC ANHYDRIDE 18-25
Dewatering agent 20-35
Triethylamine 3-6
Magnesium acetate 0.18-0.5
Wherein: dewatering agent is an acetic anhydride, and triethylamine and magnesium acetate are catalyzer.
Described acetone solvent is commercially available purity greater than 99% acetone, and the acetone solvent consumption is 100-200ml.
The methyl bismaleimides follows these steps to preparation:
(1), be 2 of 10-15 with the weight part component, 4 diaminotoluenes and weight part component are the MALEIC ANHYDRIDE of 18-25, and under normal temperature, condition of normal pressure, reaction is 0.5-1.5 hour in acetone solvent, wherein the proportioning of acetone solvent and 2,4 phenylmethylamines is 20-40: 1 milliliter/mole;
(2), at azeotropic and under the acting in conjunction of the magnesium acetate an acidic catalyst that the weight part component is the dewatering agent acetic anhydride of 20-35 and triethylamine that the weight part component is 3-6, the weight part component is 0.18-0.5, be warming up to 62-68 ℃, through reflux dewatering reaction 2-3 hour;
(3), on the rocksly be water-cooled to 6-9 ℃, add depositing in water and analysed 40 minutes, filter again after separating out crystal, wash to pH value and obtain methyl bismaleimides finished product for neutral, oven dry;
(4), the mother liquor after will filtering, washing carries out underpressure distillation, the acetone, triethylamine, the diacetyl oxide that reclaim in the mother liquor utilize once more to do circulation.
Positively effect of the present invention is:
1, can effectively improve the technology stability of span material system;
2, the methyl bismaleimides of this method preparation has high tenacity, high temperature resistant and characteristics that shock resistance is good;
3, the bismaleimide resin system that adopts the bismaleimide resin system of advanced moulding processs such as RTM, RFI for exploitation and have a high impact-resistant damage tolerance provides guarantee, has filled up domestic blank, has realized crucial raw-material autonomous guarantee.
Embodiment
Further specify the specific embodiment of the present invention below in conjunction with embodiment.
Embodiment one
18 gram MALEIC ANHYDRIDE and 100ml acetone solns are put into thermometer, agitator are housed, in the there-necked flask of water-and-oil separator, recovery prolong, under normal temperature, stir the companion, after making into homogeneous phase solution, 10 grams, 2,4 diaminotoluenes are dissolved with the 110ml acetone soln in another container, be added dropwise to then in the homogeneous phase solution that MALEIC ANHYDRIDE and acetone soln are housed, dropwised in 30 minutes, promptly generate the yellow mercury oxide that the methyl span comes amido acid, material is paste.Continue reaction after 1 hour, add 20 gram diacetyl oxides, 3 gram triethylamines, 0.18 gram magnesium acetate, heat temperature raising to 62 ℃, treat that material is transparent fully after, insulation refluxed 2 hours again, and acetone soln is reclaimed.After reaction finishes, stop heating, progressively add frozen water to solution temperature then and reach 8 ℃ in solution, the water droplet with 148ml adds in the bottle again, dropwises in 40 minutes.Separate out yellow crystals in the solution this moment, continues to stir 30 minutes, filters, is washed to neutrality, and oven dry promptly gets jonquilleous methyl bismaleimides powder finished product.
Remaining mother liquor is carried out underpressure distillation, reclaim acetone, triethylamine, diacetyl oxide is to do recycle.
Embodiment two
20 gram MALEIC ANHYDRIDE and 150ml acetone solns are put into thermometer, agitator are housed, in the there-necked flask of water-and-oil separator, recovery prolong, under normal temperature, stir the companion, after making into homogeneous phase solution, 12.5 grams, 2,4 diaminotoluenes are dissolved with the 120ml acetone soln in another container, be added dropwise to then in the homogeneous phase solution that MALEIC ANHYDRIDE and acetone soln are housed, dropwised in 45 minutes, promptly generate the yellow mercury oxide that the methyl span comes amido acid, material is paste.Continue reaction after 40 minutes, add 30 gram diacetyl oxides, 4.5 gram triethylamines, 0.3 gram magnesium acetate, heat temperature raising to 65 ℃, treat that material is transparent fully after, insulation refluxed 2.5 hours again, and acetone soln is reclaimed.After reaction finishes, stop heating, progressively add frozen water to solution temperature then and reach 7 ℃ in solution, the water droplet with 150ml adds in the bottle again, dropwises in 40 minutes.Separate out yellow crystals in the solution this moment, continues to stir 45 minutes, filters, is washed to neutrality, and oven dry promptly gets jonquilleous methyl bismaleimides powder finished product.
Remaining mother liquor is carried out underpressure distillation, reclaim acetone, triethylamine, diacetyl oxide is to do recycle.
Embodiment three
25 gram MALEIC ANHYDRIDE and 200ml acetone solns are put into thermometer, agitator are housed, in the there-necked flask of water-and-oil separator, recovery prolong, under normal temperature, stir the companion, after making into homogeneous phase solution, 15 grams, 2,4 diaminotoluenes are dissolved with the 130ml acetone soln in another container, be added dropwise to then in the homogeneous phase solution that MALEIC ANHYDRIDE and acetone soln are housed, dropwised in 60 minutes, promptly generate the yellow mercury oxide that the methyl span comes amido acid, material is paste.Continue reaction after 1 hour, add 35 gram diacetyl oxides, 6 gram triethylamines, 0.5 gram magnesium acetate, heat temperature raising to 68 ℃, treat that material is transparent fully after, insulation refluxed 3 hours again, and acetone soln is reclaimed.After reaction finishes, stop heating, progressively add frozen water to solution temperature then and reach 6 ℃ in solution, the water droplet with 158m1 adds in the bottle again, dropwises in 40 minutes.Separate out yellow crystals in the solution this moment, continues to stir 60 minutes, filters, is washed to neutrality, and oven dry promptly gets jonquilleous methyl bismaleimides powder finished product.
Remaining mother liquor is carried out underpressure distillation, reclaim acetone, triethylamine, diacetyl oxide is to do recycle.
Example detection result
Methyl bismaleimides finished product is the glassy yellow powder; Fusing point: 164-174 ℃; Impurity＜0.1%, moisture＜1%.
The above only is a non-limiting embodiment of the present invention; for the person of ordinary skill of the art; not breaking away from the invention design and not making under the prerequisite of creative work, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (3)
1. the preparation method of a methyl bismaleimides is characterized in that: the methyl bismaleimides dewater and acetone solvent outside, the weight part component of its raw material is as follows:
2,4 diaminotoluene 10-15
MALEIC ANHYDRIDE 18-25
Dewatering agent 20-35
Triethylamine 3-6
Magnesium acetate 0.18-0.5
Wherein: dewatering agent is an acetic anhydride, and triethylamine and magnesium acetate are catalyzer.
2. the preparation method of methyl bismaleimides according to claim 1 is characterized in that, described acetone solvent is commercially available purity greater than 99% acetone, and the acetone solvent consumption is 100-200ml.
3. the preparation method of methyl bismaleimides according to claim 1 is characterized in that, the methyl bismaleimides follows these steps to preparation:
(1), be 2 of 10-15 with the weight part component, 4 diaminotoluenes and weight part component are the MALEIC ANHYDRIDE of 18-25, and under normal temperature, condition of normal pressure, reaction is 0.5-1.5 hour in acetone solvent, wherein the proportioning of acetone solvent and 2,4 diaminotoluenes is 20-40: 1 milliliter/mole;
(2), at azeotropic and under the acting in conjunction of the magnesium acetate an acidic catalyst that the weight part component is the dewatering agent acetic anhydride of 20-35 and triethylamine that the weight part component is 3-6, the weight part component is 0.18-0.5, be warming up to 62-68 ℃ through cocurrent flow dehydration reaction 2-3 hour;
(3), on the rocksly be water-cooled to 6-9 ℃, add depositing in water and analysed 40 minutes, filter again after separating out crystal, wash to pH value and obtain methyl bismaleimides finished product for neutral, oven dry;
(4), the mother liquor after will filtering, washing carries out underpressure distillation, reclaim acetone, triethylamine, diacetyl oxide in the mother liquor and do circulation and utilize once more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010276983 CN101948419A (en) | 2010-09-01 | 2010-09-01 | Method for preparing methyl bismaleimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010276983 CN101948419A (en) | 2010-09-01 | 2010-09-01 | Method for preparing methyl bismaleimide |
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| Publication Number | Publication Date |
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| CN101948419A true CN101948419A (en) | 2011-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201010276983 Pending CN101948419A (en) | 2010-09-01 | 2010-09-01 | Method for preparing methyl bismaleimide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775341A (en) * | 2011-05-12 | 2012-11-14 | 咸阳三精科工贸有限公司 | Composition of N-4(anilinophenyl)maleimide and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154737A (en) * | 1976-05-05 | 1979-05-15 | E. I. Du Pont De Nemours And Company | Preparation of maleimides and dimaleimides |
| US5994561A (en) * | 1998-07-28 | 1999-11-30 | Rhein Chemie Rheinau Gmbh | Process for the preparation of aromatic maleimides |
-
2010
- 2010-09-01 CN CN 201010276983 patent/CN101948419A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154737A (en) * | 1976-05-05 | 1979-05-15 | E. I. Du Pont De Nemours And Company | Preparation of maleimides and dimaleimides |
| US5994561A (en) * | 1998-07-28 | 1999-11-30 | Rhein Chemie Rheinau Gmbh | Process for the preparation of aromatic maleimides |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Applied Polymer Science》 20041231 C. Gaina，et al. Polyimides containing 4,4'-bipyridinium units 2091-2100 1-3 第94卷, 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775341A (en) * | 2011-05-12 | 2012-11-14 | 咸阳三精科工贸有限公司 | Composition of N-4(anilinophenyl)maleimide and preparation method thereof |
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Application publication date: 20110119 |