CN113264864A - Preparation method of N, N' -m-phenylene bismaleimide - Google Patents
Preparation method of N, N' -m-phenylene bismaleimide Download PDFInfo
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- CN113264864A CN113264864A CN202110519503.XA CN202110519503A CN113264864A CN 113264864 A CN113264864 A CN 113264864A CN 202110519503 A CN202110519503 A CN 202110519503A CN 113264864 A CN113264864 A CN 113264864A
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- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 150
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 45
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 44
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 238000001704 evaporation Methods 0.000 claims description 28
- 230000008020 evaporation Effects 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 231100001231 less toxic Toxicity 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000543 intermediate Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention provides a preparation method of N, N' -m-phenylene bismaleimide, which comprises the following steps in sequence: preparing solution, synthesizing reaction, dehydrating reaction, distilling, filtering, washing, centrifugally dehydrating and drying; acetic acid is used as a solvent of maleic anhydride in the synthesis reaction, and acetone is used as a solvent of m-phenylenediamine, so that the acetic acid and the acetone are less toxic to the environment, the price is low, the environment protection is facilitated, and the production cost and the wastewater pressure are reduced; acetic anhydride is used as a dehydrating agent for dehydration reaction, and a byproduct of the dehydration reaction is acetic acid which can be recycled together with acetic acid used as a solvent, so that the production cost is reduced; the preparation method has the advantages of low reaction temperature, mild operation conditions, high reaction rate, less side reactions, stable product yield and easy industrial production.
Description
Technical Field
The invention relates to the technical field of preparation of N, N '-m-phenylene bismaleimide, in particular to a preparation method of N, N' -m-phenylene bismaleimide.
Background
N, N' -m-phenylene bismaleimide (HVA-2) is a bifunctional compound with maleimide as an active terminal, can be copolymerized with various compounds to modify into tough heat-resistant resin, and is a multifunctional rubber additive. As the multifunctional rubber additive, HVA-2 is suitable for general rubber, special rubber and rubber-plastic combined system, and can be used as a vulcanizing agent, an anti-scorching agent and a tackifier. In addition, HVA-2 can be matched with sulfur in natural rubber to prevent reversion, improve heat resistance, reduce heat generation, resist aging and improve the adhesive force between rubber and cord and the modulus of vulcanized rubber. In addition, HVA-2 is also suitable for high temperature vulcanizing system to improve crosslinking performance and raise heat resistance.
At present, the related HVA-2 synthesis methods at home and abroad are mainly as follows:
the first method is the N, N' -Dimethylformamide (DMF) method: carrying out dehydration reaction by taking DMF as a synthesis reaction solvent and anhydrous sodium acetate as a dehydration reaction catalyst; its advantage does: the DMF is a strong polar solvent, so that the reaction intermediate N, N' -m-phenylene bismaleimide acid can be dissolved in the solvent, so that a reaction system is always in a homogeneous phase state, and the reaction is favorably carried out; the disadvantages are that DMF has high price and toxicity, is not beneficial to environmental protection and energy conservation, and simultaneously the quality of the product obtained by using DMF as a solvent is extremely unstable.
The second process is the toluene process: dissolving maleic anhydride in toluene, dripping toluene solution of m-phenylenediamine, adding catalyst, refluxing and dewatering, and recovering toluene; the process is used for commercial production and has the advantages of reflux dehydration and reduction of the investment of chemical raw materials; the disadvantages are serious pollution of toluene, high boiling point (111 ℃) of the toluene and large energy consumption for recovering the toluene.
The third is the acetone process: compared with the toluene method, the method has the advantages that besides the solvent is changed from toluene to acetone, a proper amount of dehydrating agent and catalyst are added in the dehydration reaction; the advantages of this process over the toluene process are: the boiling point of acetone is 56 ℃, the acetone is easy to be recovered by distillation, so that the solvent consumption is reduced, in addition, the boiling point of acetone is lower than that of toluene, the energy consumption for recovering the acetone is lower, and the toxicity of the acetone is lower than that of the toluene, so that the pollution of the method is reduced; the method has the defects that the waste water contains a large amount of acetic acid, the COD of the waste water is high, the waste water amount is large, and the industrial production is not facilitated.
The fourth process is an acetic acid process: the method adopts acetic acid as a solvent of maleic anhydride and m-phenylenediamine, uses acetic anhydride as a dehydrating agent for dehydration reaction, and finally recovers the acetic acid in the wastewater after the reaction as the solvent of the maleic anhydride and the m-phenylenediamine in the later reaction; the method has the advantages that acetic anhydride generates by-product acetic acid in the process of cyclodehydration and acetic acid used as solvent can be recycled by distillation, thereby reducing production cost, avoiding using toxic solvents such as benzene and the like and being beneficial to environmental protection; the method has the disadvantages that through experimental study, the solubility of the m-phenylenediamine in acetic acid at normal temperature is low, if the m-phenylenediamine is completely dissolved in the acetic acid, the system temperature needs to be properly raised, and the reaction temperature needs to be strictly controlled in the first step of synthesis reaction, so that the operation is complex, and the method is not beneficial to the large-scale synthesis of HVA-2 products.
The synthetic route for HVA-2 is as follows:
(1) synthesizing N, N' -m-phenylene bismaleimide acid;
(2) the N, N '-m-phenylene bismaleimide acid generates N, N' -m-phenylene bismaleimide and water after dehydration reaction.
Disclosure of Invention
The invention aims to provide a preparation method of N, N' -m-phenylene bismaleimide, which takes acetone as a solvent of m-phenylenediamine and acetic acid as a solvent of maleic anhydride, recovers the acetone by distillation, and recovers the acetic acid by filtration, thereby reducing the production cost, reducing the energy consumption and pollution, and improving the product yield and the melting point.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of N, N' -m-phenylene bismaleimide comprises the following steps of:
1) dissolving maleic anhydride in acetic acid, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving m-phenylenediamine in acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
3) and (3) dehydration reaction: adding a dehydrating agent and a catalyst into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
Preferably, in step 1), the mass of acetic acid: the mass of the maleic anhydride is (2-4) 1; the mass of acetone: the mass of the m-phenylenediamine is (1-3) and (1).
Preferably, in the step 2), the amount of the maleic anhydride to the m-phenylenediamine is (2-2.5) to 1.
Preferably, in the step 2), the dropwise addition is completed within 1-2 h in the dropwise addition process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 0.5-1 h.
Preferably, in the step 3), the dehydrating agent is acetic anhydride, and the amount of the dehydrating agent is 1 to 1 (2.5 to 3).
Preferably, in the step 3), the catalyst is anhydrous sodium acetate, and the amount of the substance of the catalyst, that is, the amount of the substance of m-phenylenediamine (0.010-0.020) is 1.
Preferably, in the step 3), the reaction temperature of the dehydration reaction is 55-65 ℃, and the reaction time of the dehydration reaction is 3-5 h.
Preferably, in step 4), the evaporation temperature during distillation is 55 ℃ to 65 ℃.
The application obtains the following beneficial technical effects:
(1) in the synthesis reaction, acetic acid is used as a solvent of maleic anhydride, and acetone is used as a solvent of m-phenylenediamine, so that compared with the prior art in which toluene is used as a solvent of the synthesis reaction, the acetic acid and the acetone have the advantages of less toxicity to the environment and low price, thereby being beneficial to environmental protection and greatly reducing the production cost; compared with the prior art in which single acetone is used as a reaction solvent, the method greatly reduces the wastewater pressure and the production cost.
(2) According to the method, acetic acid and acetone are used as a composite solvent for synthesis reaction, acetic anhydride is used as a dehydrating agent for dehydration reaction, a byproduct of the dehydration reaction is acetic acid, and the acetic acid used as a solvent can be recycled together, so that the production cost is reduced.
(3) The preparation method provided by the application has the advantages of low reaction temperature, mild operation conditions, high reaction rate, less side reactions, stable product yield and easiness in industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The application provides a preparation method of N, N' -m-phenylene bismaleimide, which comprises the following steps in sequence:
1) dissolving maleic anhydride in acetic acid, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving m-phenylenediamine in acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
3) and (3) dehydration reaction: adding a dehydrating agent and a catalyst into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
In one embodiment of the present application, in step 1), the mass of acetic acid: the mass of the maleic anhydride is (2-4) 1; the mass of acetone: the mass of the m-phenylenediamine is (1-3) and (1).
In one embodiment of the application, in the step 2), the amount of the substance of the maleic anhydride, that is, the amount of the substance of the m-phenylenediamine (2-2.5): 1.
In one embodiment of the application, in the step 2), the dropwise addition is completed within 1h to 2h in the dropwise addition process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 0.5-1 h.
In one embodiment of the application, in the step 3), the dehydrating agent is acetic anhydride, and the amount of the dehydrating agent is 1 to 2.5 to 3.
In one embodiment of the application, in the step 3), the catalyst is anhydrous sodium acetate, and the amount of the substance of the catalyst, that is, the amount of the substance of m-phenylenediamine (0.010-0.020) is 1.
In one embodiment of the present application, in step 3), the reaction temperature of the dehydration reaction is 55 ℃ to 65 ℃, and the reaction time of the dehydration reaction is 3h to 5 h.
In one embodiment of the present application, the evaporation temperature during distillation in step 4) is between 55 ℃ and 65 ℃.
Methods and devices not described in detail in the present invention are all the prior art and are not described in detail.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of N, N' -m-phenylene bismaleimide provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
A preparation method of N, N' -m-phenylene bismaleimide comprises the following steps of:
1) placing 19.95g of maleic anhydride into a 500mL flask, adding 63g of acetic acid, stirring and dissolving, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving 10g of m-phenylenediamine in 20g of acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
in the step 2), finishing the dripping within 1-2 h in the dripping process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 1 h;
3) and (3) dehydration reaction: adding 26.43g of acetic anhydride and 0.12g of anhydrous sodium acetate into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
in the step 3), the reaction temperature of the dehydration reaction is 55 ℃, and the reaction time of the dehydration reaction is 4 hours;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
in the step 4), the evaporation temperature in the distillation process is 55-65 ℃;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
Through detection and measurement, the N, N' -m-phenylene bismaleimide prepared in example 1 has the mass of 22.5g, the yield of 90.80 percent, the appearance of yellow powder and the melting point of 201.3 ℃.
Example 2
A preparation method of N, N' -m-phenylene bismaleimide comprises the following steps of:
1) placing 19.95g of maleic anhydride into a 500mL flask, adding 63g of acetic acid, stirring and dissolving, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving 10g of m-phenylenediamine in 20g of acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
in the step 2), finishing the dripping within 1-2 h in the dripping process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 1 h;
3) and (3) dehydration reaction: adding 26.43g of acetic anhydride and 0.12g of anhydrous sodium acetate into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
in the step 3), the reaction temperature of the dehydration reaction is 60 ℃, and the reaction time of the dehydration reaction is 4 hours;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
in the step 4), the evaporation temperature in the distillation process is 55-65 ℃;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
Through detection and measurement, the N, N' -m-phenylene bismaleimide prepared in example 2 has the mass of 23g, the yield of 92.82%, the appearance of yellow powder and the melting point of 201.7 ℃.
Example 3
A preparation method of N, N' -m-phenylene bismaleimide comprises the following steps of:
1) placing 19.95g of maleic anhydride into a 500mL flask, adding 63g of acetic acid, stirring and dissolving, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving 10g of m-phenylenediamine in 20g of acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
in the step 2), finishing the dripping within 1-2 h in the dripping process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 1 h;
3) and (3) dehydration reaction: adding 26.43g of acetic anhydride and 0.12g of anhydrous sodium acetate into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
in the step 3), the reaction temperature of the dehydration reaction is 65 ℃, and the reaction time of the dehydration reaction is 4 hours;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
in the step 4), the evaporation temperature in the distillation process is 55-65 ℃;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
Through detection and measurement, the N, N' -m-phenylene bismaleimide prepared in example 3 has the mass of 22.65g, the yield of 91.40%, the appearance of yellow powder and the melting point of 200.9 ℃.
Example 4
A preparation method of N, N' -m-phenylene bismaleimide comprises the following steps of:
1) placing 19.95g of maleic anhydride into a 500mL flask, adding 63g of acetic acid, stirring and dissolving, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving 10g of m-phenylenediamine in 20g of acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
in the step 2), finishing the dripping within 1-2 h in the dripping process;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 1 h;
3) and (3) dehydration reaction: adding 26.43g of acetic anhydride and 0.12g of anhydrous sodium acetate into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
in the step 3), the reaction temperature of the dehydration reaction is 60 ℃, and the reaction time of the dehydration reaction is 4 hours;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
in the step 4), the evaporation temperature in the distillation process is 55-65 ℃;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
Through detection and measurement, the N, N' -m-phenylene bismaleimide prepared in example 4 has the mass of 22.73g, the yield of 91.73 percent, the appearance of yellow powder and the melting point of 201.8 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. A preparation method of N, N' -m-phenylene bismaleimide is characterized by comprising the following steps of:
1) dissolving maleic anhydride in acetic acid, and uniformly mixing to obtain an acetic acid solution of maleic anhydride;
dissolving m-phenylenediamine in acetone, and uniformly mixing to obtain an acetone solution of the m-phenylenediamine;
2) and (3) synthesis reaction: dripping an acetone solution of m-phenylenediamine into an acetic acid solution of maleic anhydride, carrying out a synthetic reaction on the m-phenylenediamine and the maleic anhydride to generate N, N' -m-phenylene bismaleimide acid, and obtaining an intermediate mixed solution A after the synthetic reaction is finished;
3) and (3) dehydration reaction: adding a dehydrating agent and a catalyst into the intermediate mixed solution A obtained in the step 2), carrying out dehydration reaction on N, N '-m-phenylene bismaleimide acid to generate N, N' -m-phenylene bismaleimide, and obtaining an intermediate mixed solution B after the dehydration reaction is finished;
4) and (3) distillation: distilling the intermediate mixed solution B obtained in the step 3), condensing vapor generated by evaporation to obtain condensate, recovering acetone from the condensate, and obtaining the residual liquid after evaporation;
5) and (3) filtering: filtering the residual evaporation solution obtained in the step 4), obtaining filter residues and filtrate after filtering, and recovering acetic acid from the filtrate;
6) and (3) sequentially washing, centrifugally dewatering and drying the filter residue obtained in the step 5), and obtaining powdery N, N' -m-phenylene bismaleimide after drying.
2. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 1), the mass of the acetic acid is as follows: the mass of the maleic anhydride is (2-4) 1; the mass of acetone: the mass of the m-phenylenediamine is (1-3) and (1).
3. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 2), the amount of the maleic anhydride to the m-phenylenediamine is 2-2.5 to 1.
4. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 2), the dropwise addition is completed within 1h to 2 h;
the reaction temperature of the synthesis reaction is 18-30 ℃, and the reaction time of the synthesis reaction is 0.5-1 h.
5. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 3), the dehydrating agent is acetic anhydride, and the amount of the dehydrating agent is equal to (2.5-3): 1.
6. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 3), the catalyst is anhydrous sodium acetate, and the amount of the catalyst is equal to (0.010-0.020) 1.
7. The method for preparing N, N' -m-phenylene bismaleimide according to claim 1, wherein in the step 3), the reaction temperature of the dehydration reaction is 55 ℃ to 65 ℃, and the reaction time of the dehydration reaction is 3h to 5 h.
8. The method for preparing N, N' -m-phenylene dimaleimide according to claim 1, wherein the evaporation temperature during the distillation in step 4) is 55-65 ℃.
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