CN101941935B - Method for preparing 2,2-bi[4-(2-trifluoromethyl-4-maleimidephenoxy)phenyl] hexafluoropropane - Google Patents
Method for preparing 2,2-bi[4-(2-trifluoromethyl-4-maleimidephenoxy)phenyl] hexafluoropropane Download PDFInfo
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- CN101941935B CN101941935B CN 201010287725 CN201010287725A CN101941935B CN 101941935 B CN101941935 B CN 101941935B CN 201010287725 CN201010287725 CN 201010287725 CN 201010287725 A CN201010287725 A CN 201010287725A CN 101941935 B CN101941935 B CN 101941935B
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Abstract
The invention discloses a method for preparing 2,2-bi[4-(2-trifluoromethyl-4-maleimidephenoxy)phenyl] hexafluoropropane. The method mainly comprises the following steps of: (1) reacting 2,2-bi[4-(2-trifluoromethyl-4-aminophenoxy)phenyl] hexafluoropropane with maleic anhydride in an organic solvent system for one hour at room temperature to obtain a 2,2-bi[4-(2-trifluoromethyl-4-carboxylbuteneacylaminophenoxy)phenyl] hexafluoropropane solution; (2) adding anhydrous calcium chloride solid powder, an azeotropic dehydrating agent and N,N-dimethylaniline, and heating for refluxing and a water distribution reaction; after 2-3 hours, distilling out the azeotropic dehydrating agent; cooling and dripping alcohol while stirring; and separating out a solid product to obtain 2,2-bi[4-(2-trifluoromethane-4-maleimidephenoxy)phenyl] hexafluoropropane powder. The invention has the advantages of simple operation process, high yield, less three wastes and environmental protection and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of organic cpds, particularly relate to 2, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-.
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 not following 20 kinds of commercial BMI resin prepreg material widely abroad.
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.
2; Two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-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; 2; Two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-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 2; The high heat resistance Thermocurable polyimide material for preparing, the epoxy-bismaleimide resin system of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-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.
Summary of the invention
The purpose of this invention is to provide a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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 2, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-comprises:
(1) mol ratio be 1.0: 2.0～2.1 2; Two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas of 2-and maleic anhydride are in organic solvent system; Reaction is 1 hour under the room temperature; Obtain 2, two [4-(2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) phenyl] the HFC-236fa solution of 2-;
(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 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] the HFC-236fa powder of 2-.
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, the weight sum of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas of 2-.
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 2 described in the step (2), the ratio of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa weight of 2-is 5 milliliters-10 milliliters: 1 gram.
Beneficial effect
(1) the present invention is preparation 2, the commercial run of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas (production of Shanghai EMST Electron Material Co., Ltd) of (6) 2,2-and maleic anhydride, cost is lower, is convenient to further apply.
Description of drawings
Fig. 1 is 2, the molecular structural formula of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-;
Fig. 2 is 2 of embodiment 1, the DSC collection of illustrative plates of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-;
Fig. 3 is 2, the FTIR collection of illustrative plates of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-(being positioned at the green spectrogram of intermediary).
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.
Embodiment 1
With 65.4 gram (0.1 moles) 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas (BAPFP-2TF) of 2-and 260 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 2, two [4-(2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMA) solution of 2-; 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 327 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 81.2 grams 2, (theoretical yield: 81.4 grams), yield is 99.8% to two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-.
Products therefrom is carried out test analysis characterize, the result is following:
(1) ultimate analysis: molecular formula C
37H
18F
12N
2O
6, molecular weight is 814, calculated value is C%=54.54%, H%=2.21%, F%=28.01%, N%=3.44%, O%=11.80%; Measured value is C%=55.10%, H%=2.02%, F%=27.74%, N%=3.62%.This and 2, the molecular structure of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-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 81.1 ℃, explains that it is an one matter, and fusing point is 81.1 ℃, and has higher purity; In addition, 320.1 ℃ of exothermic peaks of locating to have a broad, explain that it near 320.1 ℃ 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, the molecular structure of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-conforms to.
(3) the FTIR spectrogram of fourier transform infrared spectroscopy (being positioned at the green spectrogram of intermediary) as shown in Figure 3 has tangible imide ring (1721cm
-1, 1609cm
-1), phenyl ring (1498cm
-1), carbon-carbon double bond (1439cm
-1, 1403cm
-1), aryl oxide key (1251cm
-1, 1205cm
-1), trifluoromethyl (1321cm
-1) charateristic avsorption band.This and 2, the molecular structure of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-conforms to.
(4) aggregation test:
Get 10.0 grams 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-, 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 35MPa.
Embodiment 2
With 65.4 gram (0.1 moles) 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas (BAPFP-2TF) of 2-, 60 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 700 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 2, two [4-(2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMA) solution of 2-; 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 654 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 80.9 grams 2, (theoretical yield: 81.4 grams), yield is 99.4% to two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-.
The comparative example 1
With 65.4 gram (0.1 moles) 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas (BAPFP-2TF) of 2-, 760 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 2, two [4-(2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMA) solution of 2-; 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 654 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 63.3 grams 2, (theoretical yield: 81.4 grams), yield is 77.8% to two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa (BAPFP-2TF-BMI) powder of 2-.
Claims (8)
1.2 the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-comprises:
(1) mol ratio be 1.0: 2.0～2.1 2; Two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas of 2-and maleic anhydride are in organic solvent system; Reaction is 1 hour under the room temperature; Obtain 2, two [4-(2-trifluoromethyl-4-carboxylic crotonamide phenoxyl) phenyl] the HFC-236fa solution of 2-;
(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 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] the HFC-236fa powder of 2-.
2. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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 12; The preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-; 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, the weight sum of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fas of 2-.
4. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-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 12; The preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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 12; The preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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 12, the preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-, 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 12; The preparation method of two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fas of 2-; It is characterized in that: the ethanol volume and 2 described in the step (2), the ratio of two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] the HFC-236fa weight of 2-is 5 milliliters-10 milliliters: 1 gram.
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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 | Polypropylene acid imide foam material and preparation thereof |
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|---|---|---|---|---|
| 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 | Polypropylene acid imide foam material and preparation thereof |
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| Title |
|---|
| JP特开平6-116236A 1994.04.26 |
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