CN1775775A - Method for preparing dimaleimide compounds - Google Patents
Method for preparing dimaleimide compounds Download PDFInfo
- Publication number
- CN1775775A CN1775775A CN 200510019907 CN200510019907A CN1775775A CN 1775775 A CN1775775 A CN 1775775A CN 200510019907 CN200510019907 CN 200510019907 CN 200510019907 A CN200510019907 A CN 200510019907A CN 1775775 A CN1775775 A CN 1775775A
- Authority
- CN
- China
- Prior art keywords
- bismaleimide compound
- preparation
- maleic anhydride
- compound according
- water
- 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.)
- Pending
Links
Abstract
The invention relates to a method for preparing bismaleimide compound, mainly using diamine with NH2-R-NH2 structure to directly make one-off catalytic dehydration closed loop reaction with maleic anhydride so as to generate the bismaleimide compound. Because the reacting system is in uniform phase all along, the invention does not produce resin viscous matter, making the yield relatively stable and raising the melting point and narrowing the melting range. It has simple synthesizing route, and adopts recoverable organic solvent, reducing the three wastes, and beneficial to reduce the production cost, and it is a better industrialized production route.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of bismaleimide compound, belong to chemical field.
Background technology
Bismaleimides (BMI) is to be a class bifunctional compound of active end group with the maleimide, can be the toughness heat stable resin with multiple compound modification by copolymerization.Give this resinoid with high temperature resistant, multiple excellent properties such as moisture-proof is warm, radiation hardness, high insulation, fire-retardant, rub resistance because of its main chain contains aromatic ring and nitrogen heterocyclic structure, be widely used in fields such as national defence, aerospace, electronics, motor.For many years, in order to reduce production costs, stabilized product quality, people have carried out continuous exploration and improvement on BMI monomer synthesis technique.
At present, the synthetic method of BMI has haply both at home and abroad:
(1) Tripathi V S etc. is with N, and dinethylformamide (DMF) intensive polar solvent is a reaction medium, is catalyzer with the sodium acetate, and diacetyl oxide is a water absorbent, about 90 ℃, carry out dehydration reaction (J.PolymerSci, 1997,66:1613-1619).Be characterized in that intermediate product bismaleimide amino acid (BMIA) is dissolved in the solvent, reaction system is in homogeneous phase all the time, help reaction and carry out, but solvent toxicity is big, the price height.This reaction yield height, but poor product quality are if must purify to it as advanced composite resin matrix.
(2) Balasfalvy etc. is a solvent with acetone, nickelous acetate is a catalyzer, and diacetyl oxide is a dewatering agent, under refluxad carries out (US:4138406), be characterized in: intermediate product bismaleimide amino acid (BMIA) becomes solid to separate out from solvent, reaction is difficult for evenly, and solvent is difficult for reclaiming, and industrial production is seriously polluted, but catalyst selectivity is good, by product is few, the solvent low price, and toxicity is low.
(3) Melissaris A P etc. adopts hot dehydration closed-loop method (J Polym.Sci.:Part A:Polym.Chem.1988, V26,1165-1178.), do not add catalyzer, with strong polarity high boiling solvent, as DMF, under reflux state, react, its feature is: reaction system is in homogeneous phase all the time, the productive rate height, and three waste discharge is few.But owing to adopt high boiling solvent, system is easy to generate arborescens stickiness by product.
(4) Feng Liqi etc. makes solvent with toluene, adopts two step component distillation evaporations (macromolecular material, 1997,4 (2): 51-55), add the solvent that a kind of energy and water form azeotrope in reaction intermediate BMIA, as toluene.In the hot closed loop of catalyzer, the azeotrope of water and solvent is distilled out reactor.Be characterized in: the separated from solvent that not only steams can reuse after reclaiming, and since water constantly steam the carrying out of having accelerated hot ring-closure reaction.Reduced the three wastes, products production efficient improves greatly, and production cost is minimized, and the quality of product also is greatly improved simultaneously, but reaction system is difficult for evenly being easy to generate light brown arborescens stickies under heating condition.
The research of China BMI and commercialization are started in the seventies in 20th century, so far has only ditane type BMI product, its synthetic method mainly adopts acetone method and toluene method, because these two kinds of methods all are the reactions of carrying out in nonhomogeneous system, the part is easy to generate superheating phenomenon, the polymerization of two keys in the system that induces reaction, produce brown resin shape stickies, make final synthetic unstable product quality, fusing point is on the low side, and the melting range broad does not reach the index of export requirement.Owing to produce the environmental pollution that by product causes, Yuan Li etc. have carried out comprehensive processing and utilization to its by product, and (thermosetting resin, 2003,18 (4): 16-19), but this processing mode is cured the symptoms, not the disease in order to overcome.
Summary of the invention
The technical problem that the present invention mainly solves is: in order to overcome the deficiency that above-mentioned technology exists, provide a kind of preparation method who directly carries out the synthetic bismaleimide compound of step catalytic dehydration ring-closure reaction under the homogeneous reaction condition.This method is because reaction system is in homogeneous phase all the time, and generation tree smectic stickies does not make product yield more stable, has improved the fusing point of product, and melting range narrows down, and high performance liquid chromatography detects its relative content more than 98%.The recyclable utilization of solvent that this synthesis technique adopts has reduced the three wastes, has reduced cost.
Technical scheme of the present invention: will have NH
2-R-NH
2The diamines of structure and maleic anhydride directly carry out step catalytic dehydration ring-closure reaction under the homogeneous reaction condition in organic solvent, under catalyzer and the inhibitor action.May further comprise the steps:
(1) maleic anhydride, organic solvent and the stopper adding that measures had in the there-necked flask of thermometer, water trap, reflux condensing tube and dropping funnel, heated and stirred, the dissolving back adds catalyzer.
(2) will have NH
2-R-NH
2The diamines of structure is dissolved in N, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel.
(3) being heated to reflux temperature when temperature, beginning to drip, drip off in 2 hours, refluxes in the limit, and the limit is by water trap reaction dehydration.After dripping end, continue reflux dewatering 2 hours, stop heating then.
(4) to be cooled reaction solution being poured into during to 80 ℃-100 ℃ in 50 ℃-100 ℃ the hot water left standstill 0.5 hour, poured upper organic phase in water chromatography, and suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry obtains the bismaleimide compound crude product again.
(5) with bismaleimide compound crude product heating for dissolving in toluene, with 50 ℃-100 ℃ hot wash, separate, with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets the bismaleimide compound product.
Described have a NH
2-R-NH
2The diamines of structure, the R in its structure comprises:
Deng.
Temperature of reaction is between 25 ℃～150 ℃ in the dehydration closed-loop reaction process, maleic anhydride with have NH
2-R-NH
2The molar ratio of the diamines of structure is between 2.0～2.4, and the mass ratio of organic solvent and maleic anhydride is between 3～20 times, and the stopper consumption is 0.01%～2% of a maleic anhydride consumption, and catalyst consumption is 1%～20% of a maleic anhydride consumption.
Described catalyzer is selected sulfuric acid, acetate, phosphoric acid, nitric acid, hydrochloric acid, tosic acid or their mixture for use.
Described organic solvent is selected benzene,toluene,xylene, N for use, dinethylformamide, N,N-DIMETHYLACETAMIDE, methane amide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, acetone or their mixture.
Described stopper is selected Polyphenols or phosphorous acid esters for use.
Embodiment
Embodiment 1
17.8g (0.182mol) maleic anhydride, 100ml toluene and the adding of 10mg Resorcinol are had in the there-necked flask of thermometer, water trap, reflux condensing tube and dropping funnel, after the stirring heating dissolving, add the 1g tosic acid and the 6g vitriol oil.With 15g (0.076mol) 4,4 '-diaminodiphenylmethane is dissolved in 10ml N, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel.When temperature is heated to reflux temperature, begin to drip, drip off in 2 hours, continue to keep refluxing 2 hours, stop heating then.To be cooledly reaction solution is poured in 70 ℃ of hot water during to 100 ℃, leave standstill 0.5 hour after, pour upper organic phase in water chromatography, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets 26.35g deep yellow N, N '-4, and 4 '-diphenyl methane dimaleimide crude product, fusing point: 152～158 ℃, yield: 96.84%.
In 100ml toluene, 70 ℃ of hot washes separate with the crude product heating for dissolving, and with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets the faint yellow N of 24.86g, N '-4, and 4 '-diphenyl methane dimaleimide, fusing point: 158～160 ℃, yield: 91.36%.The relative proportion that high performance liquid chromatography detects its product peak is 98.3%.
Embodiment 2
17.8g (0.182mol) maleic anhydride, 100ml dimethylbenzene and the adding of 20mg triphenyl phosphite are had in the there-necked flask of thermometer, water trap, reflux condensing tube and dropping funnel, after the stirring heating dissolving, add 1g tosic acid and 12g 37% hydrochloric acid.With 15g (0.076mol) 4,4 '-diaminodiphenylmethane is dissolved in 10ml N, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel.When temperature is heated to reflux temperature, begin to drip, drip off in 2 hours, continue to keep refluxing 2 hours, stop heating then.To be cooledly reaction solution is poured in 100 ℃ of hot water during to 80 ℃, leave standstill 0.5 hour after, pour upper organic phase in water chromatography, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets 20.5g deep yellow N, N '-4, and 4 '-diphenyl methane dimaleimide crude product, fusing point: 151～159 ℃, yield: 75.27%.
In 100ml toluene, 100 ℃ of hot washes separate with the crude product heating for dissolving, and with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets the faint yellow N of 18.6g, N '-4, and 4 '-diphenyl methane dimaleimide, fusing point: 156～160 ℃, yield: 68.3%.The relative proportion that high performance liquid chromatography detects its product peak is 97.1%.
Embodiment 3
With 17.8g (0.182mol) maleic anhydride, 100ml toluene and 150mg 2,6 DI-tert-butylphenol compounds add and have in the there-necked flask of thermometer, water trap, reflux condensing tube and dropping funnel, after the stirring heating dissolving, add the 1g tosic acid and the 6g vitriol oil.10.3g (0.076mol) m-xylene diamine is dissolved in 10mlN, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel.When temperature is heated to reflux temperature, begin to drip, drip off in 2 hours, continue to keep refluxing 2 hours, stop heating then.To be cooledly reaction solution is poured in 70 ℃ of hot water during to 100 ℃, leave standstill 0.5 hour after, pour upper organic phase in water chromatography, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets 16.62g deep yellow 1, two (maleimide methyl) the benzene crude products of 3-, and fusing point: 120～128 ℃, yield: 73.87%.
In 100ml toluene, 70 ℃ of hot washes separate with the crude product heating for dissolving, and with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, oven dry again, 14.8g is faint yellow 1, two (maleimide methyl) benzene of 3-, fusing point: 125～129 ℃, yield: 65.78%.
Embodiment 4
15.6g (0.16mol) maleic anhydride, 100ml dimethylbenzene and the adding of 150mg diisooctyl phenyl phosphite are had in the there-necked flask of thermometer, water trap, reflux condensing tube and dropping funnel, after the stirring heating dissolving, add 1g tosic acid and 4g acetate.With 15g (0.076mol) 4,4 '-diaminodiphenylmethane is dissolved in 10mlN, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel.When temperature is heated to reflux temperature, begin to drip, drip off in 2 hours, continue to keep refluxing 2 hours, stop heating then.To be cooledly reaction solution is poured in 80 ℃ of hot water during to 90 ℃, leave standstill 0.5 hour after, pour upper organic phase in water chromatography, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets 21.4g deep yellow N, N '-4, and 4 '-diphenyl methane dimaleimide crude product, fusing point: 151～157 ℃, yield: 76.6%.
In 100ml toluene, 80 ℃ of hot washes separate with the crude product heating for dissolving, and with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets the faint yellow N of 19.3g, N '-4, and 4 '-diphenyl methane dimaleimide, fusing point: 157～160 ℃, yield: 70.9%.
Claims (9)
1, a kind of preparation method of bismaleimide compound is characterized in that and will have NH
2-R-NH
2The diamines of structure and maleic anhydride directly carry out step catalytic dehydration ring-closure reaction under the homogeneous reaction condition in organic solvent, under catalyzer and the inhibitor action; May further comprise the steps:
(1) maleic anhydride, organic solvent and stopper are added in the there-necked flask, heated and stirred, the dissolving back adds catalyzer;
(2) will have NH
2-R-NH
2The diamines of structure is dissolved in N, in the mixed solvent of dinethylformamide and toluene, pours in the dropping funnel;
(3) being heated to reflux temperature when temperature, beginning to drip, refluxes in the limit, and the limit is by water trap reaction dehydration, drip finish after, continue reflux dewatering, stop heating then;
When (4) being cooled to 80 ℃-100 ℃ reaction solution poured in 50 ℃-100 ℃ the hot water, leave standstill, pour upper organic phase in water chromatography, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry obtains the bismaleimide compound crude product again;
(5) with bismaleimide compound crude product heating for dissolving in toluene, with 50 ℃ of-100 ℃ of hot washes, separate, with upper organic phase chromatography in water, suction filtration, filter cake are used ethanol, NaHCO respectively
3The aqueous solution, water clean, and oven dry again gets the bismaleimide compound product.
2, the preparation method of a kind of bismaleimide compound according to claim 1, it is characterized in that organic solvent selects benzene,toluene,xylene, N for use, dinethylformamide, N,N-DIMETHYLACETAMIDE, methane amide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, acetone or their mixture.
3, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that catalyzer selects sulfuric acid, acetate, phosphoric acid, nitric acid, hydrochloric acid, tosic acid or their mixture for use.
4, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that dehydration closed-loop reaction response temperature is between 25 ℃～150 ℃.
5, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that maleic anhydride and has NH
2-R-NH
2The molar ratio of the diamines of structure is between 2.0～2.4.
6, the preparation method of a kind of bismaleimide compound according to claim 1, the mass ratio that it is characterized in that organic solvent and maleic anhydride is between 3～20 times.
7, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that stopper selects Polyphenols or phosphorous acid esters for use.
8, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that the stopper consumption is 0.01%～2% of a maleic anhydride consumption.
9, the preparation method of a kind of bismaleimide compound according to claim 1 is characterized in that catalyst consumption is 1%～20% of a maleic anhydride consumption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510019907 CN1775775A (en) | 2005-11-29 | 2005-11-29 | Method for preparing dimaleimide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510019907 CN1775775A (en) | 2005-11-29 | 2005-11-29 | Method for preparing dimaleimide compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1775775A true CN1775775A (en) | 2006-05-24 |
Family
ID=36765512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510019907 Pending CN1775775A (en) | 2005-11-29 | 2005-11-29 | Method for preparing dimaleimide compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1775775A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928116A (en) * | 2017-02-22 | 2017-07-07 | 濮阳市高新技术创业服务中心 | 2,2 ' double ［ 4（4 maleimide phenoxyls）Phenyl ］ propane preparation method |
| CN109851545A (en) * | 2018-12-10 | 2019-06-07 | 江苏华星新材料科技股份有限公司 | A kind of N, the preparation method of N '-penylene bismaleimide |
| CN112457332A (en) * | 2020-11-18 | 2021-03-09 | 深圳飞扬兴业科技有限公司 | Water-based high-temperature-resistant epoxy resin and preparation method thereof |
| CN113024774A (en) * | 2021-03-18 | 2021-06-25 | 三棵树(上海)新材料研究有限公司 | Epoxy curing agent containing maleimide structure and preparation method thereof |
-
2005
- 2005-11-29 CN CN 200510019907 patent/CN1775775A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928116A (en) * | 2017-02-22 | 2017-07-07 | 濮阳市高新技术创业服务中心 | 2,2 ' double ［ 4（4 maleimide phenoxyls）Phenyl ］ propane preparation method |
| CN109851545A (en) * | 2018-12-10 | 2019-06-07 | 江苏华星新材料科技股份有限公司 | A kind of N, the preparation method of N '-penylene bismaleimide |
| CN112457332A (en) * | 2020-11-18 | 2021-03-09 | 深圳飞扬兴业科技有限公司 | Water-based high-temperature-resistant epoxy resin and preparation method thereof |
| CN113024774A (en) * | 2021-03-18 | 2021-06-25 | 三棵树(上海)新材料研究有限公司 | Epoxy curing agent containing maleimide structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367774A (en) | Fluorenyl bi-benzoxazine monomer and method of preparing the same | |
| CN101200822A (en) | Polyimide fibre containing benzimidazole structure and preparation method thereof | |
| CN109679048B (en) | Main chain type benzoxazine resin and preparation method thereof | |
| CN104892484A (en) | Synthesis method for N-phenylmaleimide | |
| CN1775775A (en) | Method for preparing dimaleimide compounds | |
| CN106928116B (en) | Preparation method of 2, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane | |
| CN101591299B (en) | Side imidazolyl-containing benzidine derivatives and preparation method thereof | |
| CN101429172A (en) | Fluorenyl di-benzoxazine monomer and method of preparing the same | |
| CN114805332A (en) | Bismaleimide containing oxazine side group and Cardo structure and preparation method thereof | |
| CN101921396B (en) | Semi-aryl poly (phenylene sulfide amide) and preparation method thereof | |
| CN102617857B (en) | Polyimide and preparation process thereof | |
| Wu et al. | Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly (propargylamine) s | |
| US6066743A (en) | Solventless preparation of phthalimides | |
| CN103342812A (en) | Aromatic polyamide sulfamide and preparation method thereof | |
| CN104262233B (en) | Phthalimide-containing phthalonitrile monomer and its preparation method and use | |
| EP1803705A1 (en) | Aromatic diamine and process for producing the same | |
| CN1274657C (en) | Process for preparing substituted glutaric anhydride | |
| CN109776518B (en) | Novel AB type benzoxazine monomer and preparation method thereof | |
| CN106905529A (en) | Cyano-containing and fluorenyl bimaleimide resin and preparation method thereof | |
| CN103012087B (en) | Green synthetic method of alpha, alpha'-double benzylidene cycloalkanone compound | |
| CN102942533B (en) | Preparation method of 4-(5-amino-6-hydroxy-2-benzoxazolyl) benzoic acid (ABA) | |
| Jung et al. | Synthesis, characterization and properties of polyimides from 3, 3′, 4, 4′-benzophenonetetracarboxylic dianhydride and imidazole-blocked 2, 5-bis [(n-alkyloxy) methyl]-1, 4-benzenediisocyanates | |
| CN103641741B (en) | Preparation method of pesticide intermediate malononitrile | |
| CN102603533B (en) | Preparation method of 4,4'-dinitrodiphenyl ether | |
| CN100469766C (en) | Process for preparing N-cyclohexyl maleimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |