CN101941932B - Preparation method of 1,3-bis(4-maleimido-2-trifluoromethylphenoxy)benzene - Google Patents
Preparation method of 1,3-bis(4-maleimido-2-trifluoromethylphenoxy)benzene Download PDFInfo
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Abstract
The invention discloses a preparation method for 1,3-di(4-bismaleimide-2-trifluoromethyl phenoxy) benzene, which mainly comprises the following steps of: (1) adding 1,3-di(4-anino-2-trifluoromethyl phenoxy) benzene and maleic anhydride according to the molar ratio of 1.0 to 2.0 to 2.1 to an organic solvent system and reacting for 1 hour at room temperature to prepare a 1,3-di(4-carboxy dinitramine amide-2-trifluoromethyl phenoxy) benzene solution; and (2) adding anhydrous calcium chloride solid powder, an azeotropic dehydrating agent and N, N-dimethylaniline and carrying out a heating backflow water-dividing reaction; distilling to prepare the azeotropic dehydrating agent after 2 to 3 hours; cooling to the room temperature; dropwise adding ethanol under the condition of stirring at high speed to separate out solid products; filtering; washing; and drying to prepare the 1, 3-di(4-bismaleimide-2-trifluoromethyl phenoxy) benzene powder. The preparation method has the advantages of simple operation technology, high yield, less three wastes and friendly environment, and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of organic cpds, particularly relate to 1, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-.
Background technology
People just synthesize bimaleimide resin (BMI) as far back as the forties, and as far back as 1948, American Searle just obtained the synthetic patent of BMI.After this, Searle has synthesized the BMI monomer of various different structures and performance on the basis of improving compound method.To the end of the sixties, French Rhone-Poulenc company at first develops M-33BMI resin and matrix material thereof.Early stage work mainly concentrates on the refractory glass fibre insulating material.To the later stage seventies, so that solve the problem of epoxy humidity resistance difference, just begin BMI as advanced composite material (ACM) matrix, aerospace material.Nearly two during the last ten years, and the BMI resin is developed rapidly and uses widely, not following 20 kinds of external own commercial BMI resin prepreg material.
China begins the research work of BMI the beginning of the seventies, with external early stage the same, around F level, H level fiberglass layer pressing plate and Heat-Resisting Adhesive the demand of BMI has been carried out number of research projects.Arrived the mid-80, just carried out the research of ACM successively, obtained certain scientific payoffs with the BMI resin matrix, but still bigger with the level disparity of advanced countries such as the U.S., seriously hinder the development of China's aviation matrix material and aircraft of future generation, military secret.
1; Two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-are a kind of bimaleimide resins; Contain imide structure in its molecular structure; Have good thermostability, also contain undersaturated double bond structure, have quite active chemical reactivity; Can play addition reaction with containing compound bearing active hydrogen (like oxy-compound, aminocompound, carboxylic compound etc.) or polymkeric substance, the compound or the polymkeric substance that also can contain unsaturated groups such as two keys or triple bond with other carry out chemical reaction.Therefore, 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-can be used for preparing the Thermocurable polyimide material of high heat resistance, also can be used as the heat-proof modifier of epoxy resin, and make the epoxy-bismaleimide resin system of high heat resistance.
Can envision and obtain; By 1; The high heat resistance Thermocurable polyimide material for preparing, the epoxy-bismaleimide resin system of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-can further make the carbon fiber reinforced advanced composite material, can be used for the structured material of aerospacecraft (like aircraft, rocket, satellite, guided missile etc.) etc.; Also can further make glass fiber reinforced composite materials, can be used for the insulating material of printed circuit board, electrical equipment and electrical etc. etc.; The interlayer dielectic, FPC that also can make high-temperature-resistant structure tackiness agent, high-temperaure coating, electronics microelectronic device are with tackiness agent etc.
Japanese Patent JP06-116236A (1994-04-26) discloses 2; The preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-is primarily characterized in that: utilize dinitro compound, through reduction reaction; Obtain diamines; With the unsaturated acid anhydride reactant, obtain span and come amido acid solution again, utilize fatty acid anhydride to come amido acid to carry out the dehydration closed-loop reaction at last span; Obtain 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] the HFC-236fa title products of 2-.The shortcoming of this method is that yield and purity are on the low side, and the three wastes are more, and smell is big, and is high to equipment requirements.
Japanese Patent JP03-091532A (1991-04-17), JP04-280659A (1992-10-06), JP06-122736A (1994-05-06), JP11-026222A (1999-01-29) are to 2, and two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-are reported in the application of high-technology fields such as semiconducter device, magnetic core tackiness agent.
Chinese patent CN101328243A (2008-12-24) discloses polypropylene acid imide foam material and preparation method thereof; It is characterized in that: the polypropylene acid imide foam material that is provided; Be to process: the propylene class monomer 1-100 that contains carboxyl or ester group by the raw material that contains following weight part; The propylene class monomer 1-100 of nitrile group-containing, bimaleimide resin 1-100; Bimaleimide resin, acrylic monomer, vinyl cyanide monomer are formed the foam precursor multipolymer through free radical copolymerization; Form the polypropylene acid imide foam material of high strength and modulus, high heat resistance then through the heat foamable process, can be widely used in the manufacturing of the foamed sandwich structure spare of space flight, aviation, space vehicle and naval vessel, bullet train, wind power plant.
But, do not see that about 1 the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-has only reported its raw material as a kind of bimaleimide resin, the application aspect the preparation polypropylene acid imide foam material.
Chinese patent CN101463107A (2009-06-24) discloses a kind of flame retardant type polymethacrylimide foam material and preparation method thereof and application; It is characterized in that: the flame retardant type Polymethacrylimide class A foam A material that is provided is to be processed by the main raw material that contains following weight part: contain the propylene class monomer 1-100 of carboxyl or ester group, the propylene class monomer 1-100 of nitrile group-containing; Silicon-phosphorus synergistic fire retardant 1-100; Nucleator 0-25, whipping agent 0-25, linking agent 0-25; Releasing agent 0-25, bimaleimide resin 0-25; Silicon-phosphorus synergistic fire retardant, bimaleimide resin, acrylic monomer, vinyl cyanide monomer are formed the foam precursor multipolymer through free radical copolymerization; Form the polypropylene acid imide foam material of fire-retardant, high strength and modulus, high heat resistance then through the heat foamable process, can be widely used in the manufacturing of the foamed sandwich structure spare of space flight, aviation, space vehicle and naval vessel, bullet train, wind power plant.
But, do not see that about 1 the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-has only reported its raw material as a kind of bimaleimide resin, the application aspect preparation flame retardant type Polymethacrylimide class A foam A material.
Summary of the invention
The purpose of this invention is to provide a kind of 1, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, this method technology is simple, the three wastes are few, cost is low, environmental friendliness, purity and yield are high, are applicable to industrial production.
Chemical equation of the present invention is following:
The invention provides a kind ofly 1, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-comprises:
(1) mol ratio be 1.0: 2.0～2.1 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-and maleic anhydride are in organic solvent system, reaction is 1 hour under the room temperature, obtains 1,3-pair of (4-carboxylic crotonoyl amido-2-4-trifluoromethylphenopendant) benzole solns;
(2) weight ratio of adding and maleic anhydride is 1: 19～21 Calcium Chloride Powder Anhydrous pressed powder, azeotropy dehydrant and N, accelerine, and reflux is divided the water reaction, after 2～3 hours; Distill out azeotropy dehydrant, be cooled to room temperature, drip ethanol under the high-speed stirring; Separate out solid product, filter, washing; Drying obtains 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) the benzene powder of 3-.
Organic solvent described in the step (1) is strong polar non-proton organic solvent.
Preferred strong polar non-proton organic solvent is selected from N, dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, a kind of or its mixture in the DMSO 99.8MIN..
Organic solvent volume described in the step (1) is 3 milliliters～9 milliliters with the ratio of reactant weight: 1 gram, wherein, reactant weight is meant maleic anhydride and 1, the weight sum of two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-.
It is 100 ℃～160 ℃ that reflux described in the step (2) is divided the TR of water reaction.
Azeotropy dehydrant described in the step (2) is selected from a kind of or its blend in benzene,toluene,xylene, ethylbenzene, diethylbenzene, chlorobenzene, the dichlorobenzene.
Azeotropy dehydrant volume described in the step (2) is 5 milliliters～10 milliliters with the ratio of maleic anhydride weight: 1 gram.
N described in the step (2), the weight ratio of accelerine and maleic anhydride is 1: 20～40.
Ethanol volume and 1 described in the step (2), the ratio of two (4-amino-2-4-trifluoromethylphenopendant) the benzene weight of 3-is 5 milliliters-10 milliliters: 1 gram.
Beneficial effect
(1) the present invention is preparation 1, the commercial run of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, and product yield and purity are all higher;
(2) operating procedure of the present invention is simple, and the conversion unit less investment can be accomplished the preparation process in same reaction kettle;
(3) reaction process is under normal pressure, to carry out, and does not need high-tension apparatus;
(4) do not produce corrosives in reactant and the reaction process yet;
(5) after reaction is accomplished, reclaimed organic solvent, reusable edible.This has not only reduced cost, and has reduced environmental pollution;
Reaction raw materials convenient sources such as two (4-amino-2-4-trifluoromethylphenopendant) benzene (production of Shanghai EMST Electron Material Co., Ltd) of (6) 1,3-and maleic anhydride, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 1, the molecular structural formula of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-;
Fig. 2 is 1, the DSC collection of illustrative plates of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-(blue curve 2);
Fig. 3 is 1, the FTIR collection of illustrative plates (spectrogram of the top) of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-.
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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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.
With 42.8 gram (0.1 moles) 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF) of 3-and 190 milliliters of N-N-methyl-2-2-pyrrolidone N-s add in the reactor drum, stir under the room temperature; After the dissolving, add the maleic anhydride solid fully in batches, make maintain at room temperature state; Add maleic anhydride (MA) solid 20.5 grams (0.21 mole) altogether; Stirring reaction is 1 hour under the room temperature, obtains 1, two (4-carboxylic crotonoyl amido-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMA) solution of 3-; Subsequently, add 1.0 gram anhydrous chlorides of rase calcium powders, 205 milliliters of methylbenzene azeotropic dewatering agents, 1.0 gram N, accelerine stirs; Heat temperature raising after 2～3 hours, distills out methylbenzene azeotropic dewatering agent (reclaiming sharp recycle) until reflux water-dividing, is cooled to room temperature; Drip 214 milliliters of ethanol under the high-speed stirring, separate out solid product, filter; Mother liquor fractionation purification recycle, filter residue is with deionized water wash 2-3 time, drying; Obtain 58.4 grams 1, (theoretical yield: 58.8 grams), yield is 99.3% to two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-.
Products therefrom is carried out test analysis characterize, the result is following:
(1) ultimate analysis: molecular formula C
28H
14F
6N
2O
6, molecular weight is 588, calculated value is C%=57.14%, H%=2.38%, F%=19.39%, N%=4.76%, O%=16.33%; Measured value is C%=57.95%, H%=2.01%, F%=18.97%, N%=4.19%.This and 1, the molecular structure of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-conforms to.
(2) scanning curve of differential scanning calorimeter (DSC) (blue curve 2) as shown in Figure 2, it is unimodal to locate to have a sharp-pointed fusion at 167.2 ℃, explains that it is an one matter, and fusing point is 167.2 ℃, and has higher purity; In addition, 315.0 ℃ of exothermic peaks of locating to have a broad, explain that it near 315.0 ℃ of temperature thermopositive reaction can take place, this is the result of the free radical reaction that produced by thermal initiation of the two keys in the maleimide resin just.This and 1, the molecular structure of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-conforms to.
(3) the FTIR spectrogram of fourier transform infrared spectroscopy (spectrogram of the top) as shown in Figure 3 has tangible imide ring (1718cm
-1), phenyl ring (1594cm
-1, 1501cm
-1), carbon-carbon double bond (1437cm
-1, 1402cm
-1), aryl oxide key (1267cm
-1, 1237cm
-1, 1203cm
-1), trifluoromethyl (1322cm
-1) charateristic avsorption band.This and 1, the molecular structure of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-conforms to.
(4) aggregation test:
Get 10.0 grams 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-, 6.0 gram end carboxyl nitrile rubbers (Lanzhou petrochemical industry research institute of orchidization group provides) and 60.0 gram ES216 epoxy resin (oxirane values: 0.22; Shanghai EMST Electron Material Co., Ltd provides) add in the reaction kettle, after 0.5 hour, add 100.0 gram toluene solvants in 100 ℃ of stirring reactions, stir under the room temperature, obtain the thickness resin solution of homogeneous phase transparent.
Get above-mentioned resin liquid, evenly be coated on the test piece of standard stainless steel, overlap joint, thermofixation (100 ℃/1 hour+150/1 hour) gets the standard bonding sample, and recording the room temperature tensile shearing resistance is 32MPa.
Embodiment 2
With 42.8 gram (0.1 moles) 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF) of 3-, 60 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 500 milliliters of N, dinethylformamide adds in the reactor drum; Stir under the room temperature; After the dissolving, add the maleic anhydride solid fully in batches, make maintain at room temperature state; Add maleic anhydride (MA) solid 19.6 grams (0.2 mole) altogether; Stirring reaction is 1 hour under the room temperature, obtains 1, two (4-carboxylic crotonoyl amido-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMA) solution of 3-; Subsequently, add 1.0 gram anhydrous chlorides of rase calcium powders, 98 milliliters of YLENE azeotropy dehydrants, 0.5 gram N, accelerine stirs; Heat temperature raising after 2～3 hours, distills out YLENE azeotropy dehydrant (reclaiming sharp recycle) until reflux water-dividing, is cooled to room temperature; Drip 428 milliliters of ethanol under the high-speed stirring, separate out solid product, filter; Mother liquor fractionation purification recycle, filter residue is with deionized water wash 2-3 time, drying; Obtain 58.1 grams 1, (theoretical yield: 58.8 grams), yield is 98.9% to two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-.
The comparative example 1
With 42.8 gram (0.1 moles) 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF) of 3-, 560 milliliters of N, dinethylformamide adds in the reactor drum; Stir under the room temperature, after the dissolving, add the maleic anhydride solid fully in batches; Make maintain at room temperature state, add maleic anhydride (MA) solid 19.6 grams (0.2 mole) altogether, stirring reaction is 1 hour under the room temperature; Obtain 1, two (4-carboxylic crotonoyl amido-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMA) solution of 3-; Subsequently, add 98 milliliters of YLENE azeotropy dehydrants, stir, heat temperature raising is until reflux water-dividing; After 2～3 hours, distill out YLENE azeotropy dehydrant (reclaiming sharp recycle), be cooled to room temperature; Drip 428 milliliters of ethanol under the high-speed stirring, separate out solid product, filter; Mother liquor fractionation purification recycle, filter residue is with deionized water wash 2-3 time, drying; Obtain 49.1 grams 1, (theoretical yield: 58.8 grams), yield is 83.5% to two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene (DARes-2TF-BMI) powder of 3-.
Claims (8)
1.3-the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene comprises:
(1) mol ratio be 1.0: 2.0～2.1 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-and maleic anhydride are in organic solvent system, reaction is 1 hour under the room temperature, obtains 1,3-pair of (4-carboxylic crotonoyl amido-2-4-trifluoromethylphenopendant) benzole solns;
(2) weight ratio of adding and maleic anhydride is 1: 19～21 Calcium Chloride Powder Anhydrous pressed powder, azeotropy dehydrant and N, accelerine, and reflux is divided the water reaction, after 2～3 hours; Distill out azeotropy dehydrant, be cooled to room temperature, drip ethanol under the high-speed stirring; Separate out solid product, filter, washing; Drying obtains 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) the benzene powder of 3-.
2. according to claim 11, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, it is characterized in that: the organic solvent described in the step (1) is strong polar non-proton organic solvent; Be selected from N; Dinethylformamide, DMAC N,N; The N-N-methyl-2-2-pyrrolidone N-, a kind of or its mixture in the DMSO 99.8MIN..
3. according to claim 11; The preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-; It is characterized in that: the organic solvent volume described in the step (1) is 3 milliliters～9 milliliters with the ratio of reactant weight: 1 gram; Wherein, reactant weight is meant maleic anhydride and 1, the weight sum of two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-.
4. according to claim 11, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-is characterized in that: it is 100 ℃～160 ℃ that the reflux described in the step (2) is divided the TR of water reaction.
5. according to claim 11; The preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, it is characterized in that: the azeotropy dehydrant described in the step (2) is selected from a kind of or its mixture in benzene,toluene,xylene, ethylbenzene, diethylbenzene, chlorobenzene, the dichlorobenzene.
6. according to claim 11, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, it is characterized in that: the azeotropy dehydrant volume described in the step (2) is 5 milliliters～10 milliliters with the ratio of maleic anhydride weight: 1 gram.
7. according to claim 11, the preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, it is characterized in that: the N described in the step (2), the weight ratio of accelerine and maleic anhydride is 1: 20～40.
8. according to claim 11; The preparation method of two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-; It is characterized in that: the ethanol volume and 1 described in the step (2), the ratio of two (4-amino-2-4-trifluoromethylphenopendant) the benzene weight of 3-is 5 milliliters-10 milliliters: 1 gram.
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| CN109336416B (en) * | 2018-09-17 | 2021-07-30 | 常州市北洋建材有限公司 | Glass wool and preparation method thereof |
| CN113354814B (en) * | 2021-06-22 | 2023-05-05 | 中国科学院长春应用化学研究所 | Modified cyanate resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108882A (en) * | 1985-12-26 | 1987-09-09 | 三井东压化学株式会社 | The manufacture method of aromatic dimaleimide compounds |
| CN101328243A (en) * | 2007-06-20 | 2008-12-24 | 中国科学院化学研究所 | A kind of polyacrylimide foam material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3135011B2 (en) * | 1992-10-02 | 2001-02-13 | セントラル硝子株式会社 | Method for producing bisimide compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108882A (en) * | 1985-12-26 | 1987-09-09 | 三井东压化学株式会社 | The manufacture method of aromatic dimaleimide compounds |
| CN101328243A (en) * | 2007-06-20 | 2008-12-24 | 中国科学院化学研究所 | A kind of polyacrylimide foam material and preparation method thereof |
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| Title |
|---|
| JP特开平6-116236A 1994.04.26 |
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