CN101941933B - 2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene and preparation method thereof - Google Patents
2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene and preparation method thereof Download PDFInfo
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- CN101941933B CN101941933B CN 201010287442 CN201010287442A CN101941933B CN 101941933 B CN101941933 B CN 101941933B CN 201010287442 CN201010287442 CN 201010287442 CN 201010287442 A CN201010287442 A CN 201010287442A CN 101941933 B CN101941933 B CN 101941933B
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Abstract
The invention discloses 2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene and a preparation method thereof. The molecular structural formula of the 2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene is shown in the specification. The preparation method comprises the following steps of: (2) reacting 2-methyl-1,4-di(2-trifluoromethyl-4-amino phenoxyl) benzene with maleic anhydride in an organic solvent system for 1 hour at the room temperature to obtain a 2-methyl-1,4-di(2-trifluoromethyl-4-carboxyl butylene amido phenoxyl) benzene solution; and (2) adding anhydrous calcium chloride solid powder, an azeotropic dehydrating agent and N,N-dimethylaniline, heating and refluxing for water-distribution reaction, distilling the azeotropic dehydrating agent, cooling to the room temperature, dropwise adding alcohol during stirring, precipitating a solid product, filtering, washing and drying to obtain 2-methyl-1,4-di(2-trifluoromethyl-4-maleimide phenoxyl) benzene powder. The preparation method has the advantages of simple operation process, high yield, less three wastes and is environment-friendly and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of organic cpds, particularly relate to the 2-methyl isophthalic acid, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-.
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-33 BMI 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.
The 2-methyl isophthalic acid; Two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-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; The 2-methyl isophthalic acid; Two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-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 the 2-methyl isophthalic acid; The high heat resistance Thermocurable polyimide material for preparing, the epoxy-bismaleimide resin system of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-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.
But, 2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-and preparation method thereof.So far do not see as yet patent or disclosed bibliographical information are arranged.
Summary of the invention
The purpose of this invention is to provide a kind of 2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-and preparation method thereof, this method technology is simple, the three wastes are few, and cost is low, and 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 of 2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, its molecular structural formula is:
A kind of 2-methyl isophthalic acid of the present invention, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-comprises:
(1) with mol ratio is 1.0: 2.0～2.1 2-methyl isophthalic acid; Two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-and maleic anhydride are in organic solvent system; Reaction is 1 hour under the room temperature, obtains the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) benzole solns of 4-;
(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 the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) the benzene powder of 4-.
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 2-methyl isophthalic acid, the weight sum of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-.
It is 100 ℃～160 ℃ that reflux described in the step (2) is divided the TR of water reaction.
Described 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 described in the step (2) and 2-methyl isophthalic acid, the ratio of two (2-trifluoromethyl-4-amino-benzene oxygen) the benzene weight of 4-is 5 milliliters-10 milliliters: 1 gram.
Beneficial effect
(1) the present invention is a preparation 2-methyl isophthalic acid, the commercial run of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, 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;
(6) 2-methyl isophthalic acid, reaction raw materials convenient sources such as two (2-trifluoromethyl-4-amino-benzene oxygen) benzene (production of Shanghai EMST Electron Material Co., Ltd) of 4-and maleic anhydride, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is the 2-methyl isophthalic acid, the molecular structural formula of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-;
Fig. 2 is the 2-methyl isophthalic acid, the DSC collection of illustrative plates of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-;
Fig. 3 is the 2-methyl isophthalic acid, the FTIR collection of illustrative plates of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-.
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 44.2 gram (0.1 mole) 2-methyl isophthalic acids, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene (DATHQ-2TF) of 4-and 195 milliliters of DMAC N,Ns 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 the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) benzene (DATHQ-2TF-BMA) solution of 4-; 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 221 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 60.0 gram 2-methyl isophthalic acids, (theoretical yield: 60.2 grams), yield is 99.8% to two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-.
Products therefrom is carried out test analysis characterize, the result is following:
(1) ultimate analysis: molecular formula C
29H
16F
6N
2O
6, calculated value is C%=57.81%, H%=2.66%, F%=18.94%, N%=4.65%, O%=15.94%; Measured value is C%=58.12%, H%=2.45%, F%=18.77%, N%=4.70%.This and 2-methyl isophthalic acid, the molecular structure of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-conforms to.
(2) scanning curve of differential scanning calorimeter (DSC) is as shown in Figure 2, and it is unimodal to locate to have a sharp-pointed fusion at 213.0 ℃, explains that it is an one matter, and fusing point is 213.0 ℃, and has higher purity; In addition, 324.2 ℃ of exothermic peaks of locating to have a broad, explain that it near 324.2 ℃ 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 2-methyl isophthalic acid, the molecular structure of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-conforms to.
(3) the FTIR spectrogram of fourier transform infrared spectroscopy is as shown in Figure 3, has tangible imide ring (1708cm
-1, 1622cm
-1), phenyl ring (1505cm
-1, 1487cm
-1), carbon-carbon double bond (1437cm
-1, 1410cm
-1), aryl oxide key (1245cm
-1, 1187cm
-1), trifluoromethyl (1321cm
-1) charateristic avsorption band.This and 2-methyl isophthalic acid, the molecular structure of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-conforms to.
(4) aggregation test (application example):
Get 10.0 gram 2-methyl isophthalic acids, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-, 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 27MPa.
With 44.2 gram (0.1 mole) 2-methyl isophthalic acids, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene (DATHQ-2TF) of 4-, 74 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 the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) benzene (DATHQ-2TF-BMA) solution of 4-; 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 442 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 59.9 gram 2-methyl isophthalic acids, (theoretical yield: 60.2 grams), yield is 99.6% to two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-.
The comparative example 1
With 44.2 gram (0.1 mole) 2-methyl isophthalic acids, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene (DATHQ-2TF) of 4-, 74 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 the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) benzene (DATHQ-2TF-BMA) solution of 4-; 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 442 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 40.8 gram 2-methyl isophthalic acids, (theoretical yield: 60.2 grams), yield is 67.8% to two (2-trifluoromethyl-4-maleimide phenoxyl) benzene (DATHQ-2TF-BMI) powder of 4-.
Claims (9)
1.2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, its molecular structural formula is:
2. 2-methyl isophthalic acid, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-comprises:
(1) with mol ratio is 1.0: 2.0～2.1 2-methyl isophthalic acid; Two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-and maleic anhydride are in organic solvent system; Reaction is 1 hour under the room temperature, obtains the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) benzole solns of 4-;
(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 the 2-methyl isophthalic acid, two (2-trifluoromethyl-4-maleimide phenoxyl) the benzene powder of 4-.
3. a kind of 2-methyl isophthalic acid according to claim 2, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, 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..
4. a kind of 2-methyl isophthalic acid according to claim 2; The preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-; 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 2-methyl isophthalic acid, the weight sum of two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-.
5. a kind of 2-methyl isophthalic acid according to claim 2, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-is characterized in that: it is 100 ℃～160 ℃ that the reflux described in the step (2) is divided the TR of water reaction.
6. a kind of 2-methyl isophthalic acid according to claim 2; The preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, it is characterized in that: the described 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.
7. a kind of 2-methyl isophthalic acid according to claim 2; The preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, 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.
8. a kind of 2-methyl isophthalic acid according to claim 2, the preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, it is characterized in that: the N described in the step (2), the weight ratio of accelerine and maleic anhydride is 1: 20～40.
9. a kind of 2-methyl isophthalic acid according to claim 2; The preparation method of two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-; It is characterized in that: ethanol volume described in the step (2) and 2-methyl isophthalic acid, the ratio of two (2-trifluoromethyl-4-amino-benzene oxygen) the benzene weight of 4-is 5 milliliters-10 milliliters: 1 gram.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050198A (en) * | 2007-05-11 | 2007-10-10 | 东华大学 | Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane |
| CN101704989A (en) * | 2009-11-13 | 2010-05-12 | 东华大学 | Fluorine-containing imine matrix resin used for advanced composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050198A (en) * | 2007-05-11 | 2007-10-10 | 东华大学 | Method for preparing 4,4'- bi (4 - carboxyl phthalimide group) 3,3'- dimethyl diphenylmothane |
| CN101704989A (en) * | 2009-11-13 | 2010-05-12 | 东华大学 | Fluorine-containing imine matrix resin used for advanced composite material and preparation method thereof |
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| Title |
|---|
| CN 101704989 A,说明书全文. |
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