CN108976418B

CN108976418B - Three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene and preparation method thereof

Info

Publication number: CN108976418B
Application number: CN201810797156.5A
Authority: CN
Inventors: 李娟�; 王鑫君
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2018-07-19
Filing date: 2018-07-19
Publication date: 2021-01-05
Anticipated expiration: 2038-07-19
Also published as: CN108976418A

Abstract

The invention discloses a three-dimensional structure flame retardant based on a furan derivative and cyclotriphosphazene and a preparation method thereof. The structural formula of the flame retardant is shown as a formula (4). The cyclotriphosphazene and furan derivatives are subjected to nucleophilic substitution reaction to obtain an intermediate product hexafuryl cyclotriphosphazene, and the intermediate product and bismaleimide compound are subjected to Diels-Alder reaction to form the flame retardant with a three-dimensional structure. The synthetic method of the flame retardant with the three-dimensional structure is simple and easy to operate. The flame retardant with the three-dimensional structure can be used for polyvinyl acetate, polyethylene, polypropylene, polyolefin elastomer, polyurethane elastomer and the like, is compounded with ammonium polyphosphate for use, and has low addition and high flame retardant efficiency.

Description

Three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene and preparation method thereof

Technical Field

The invention belongs to the field of flame retardants, and particularly relates to a three-dimensional structure flame retardant based on a furan derivative and cyclotriphosphazene and a preparation method thereof.

Background

The high polymer material is widely applied to industrial manufacture and human life, but has certain potential safety hazard due to the flammability, so that the key to the safe use of the high polymer material is to endow the high polymer material with a flame retardant function. At present, a plurality of scholars are dedicated to research on green environment-friendly flame retardants. On one hand, although the traditional halogen flame retardant has a good flame retardant effect, a large amount of toxic gas and dense smoke can be released in the combustion process, and secondary damage is easily caused. On the other hand, with the increasing exhaustion of petroleum resources, a sustainable development direction becomes a necessary choice for current flame retardant technology. People turn their eyes to the biological world and expect to find an effective sustainable development strategy. Wherein, the flame retardant is taken as an essential additive, and the greening of the flame retardant is a necessary choice for the development of flame retardant technology. The bio-based raw material is a renewable green material and has the advantages of wide source, relatively low price, low toxicity and strong sustainability. The research on green and efficient flame retardants by taking bio-based as raw materials becomes the focus of the current research.

The phosphazene is a compound with a stable phosphorus-nitrogen framework structure, and the phosphorus-nitrogen hybrid structure has good thermal stability and flame retardant property. Meanwhile, the flame retardant has the characteristics of no halogen, less smoke and high carbon residue rate, and is a high-efficiency flame retardant raw material. Chinese patent CN201410367324 synthesizes hexaaniline cyclotriphosphazene with aniline and hexachlorocyclotriphosphazene as raw materials and chlorobenzene as solvent. In the Chinese patent CN200710051404, p-hydroxybenzaldehyde and hexachlorocyclotriphosphazene are used as raw materials, and a target product is synthesized by a series of methods. Chinese patent CN201310488939 takes sodium phenolate and hexachlorocyclotriphosphazene as raw materials, and obtains a target product through a series of chemical synthesis methods. Chinese patent CN201510248852 synthesizes naphthylamine cyclotriphosphazene from naphthalene diamine and hexachlorocyclotriphosphazene. US patent US4600791 dropwise reacts a high boiling point chloroalkane (arene) solution of hexachlorocyclotriphosphazene with an aqueous solution of phenol, potassium hydroxide and quaternary ammonium salt, after the reaction is completed, the mixture is kept stand for layering, and the product is obtained by acid washing, alkali washing, water washing, drying and solvent removal.

In conclusion, the phosphazene is a flame retardant monomer with strong designability, and has potential application prospects in various fields. Furan is a bio-based platform compound, and has characteristics comparable to those of benzene rings, so that furan becomes a hot point of research. At present, the research is mostly carried out by adopting furan dicarboxylic acid as a monomer to prepare the bio-based polyester. The furan polymer is expected to be a novel flame retardant unit due to good char forming capability, and related researches are not reported in a public way. The invention adopts cyclotriphosphazene and furan derivatives as monomers to form a multifunctional furan ring compound, and then the multifunctional furan ring compound reacts with a bismaleimide compound to prepare the novel flame retardant with a three-dimensional structure.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a three-dimensional structure flame retardant based on furan derivatives and cyclotriphosphazene. The flame retardant does not contain halogen, is green and environment-friendly, has broad spectrum and high efficiency, and is a flame retardant with excellent comprehensive performance.

The invention is realized by the following technical scheme:

the three-dimensional flame retardant based on the furan derivative and the cyclotriphosphazene has the structural characteristics shown in the formula (4):

wherein-R₁-is-O-or-NH-; -R₂-is of

－R₃-is-H or-CHO.

The invention also aims to provide a preparation method of the three-dimensional flame retardant based on the furan derivative and the cyclotriphosphazene, which comprises the following steps of carrying out nucleophilic substitution reaction on the cyclotriphosphazene and the furan derivative to obtain an intermediate product of hexafuryl cyclotriphosphazene, and carrying out Diels-Alder reaction on the intermediate product and a bismaleimide compound to form the three-dimensional flame retardant:

1) synthesis of hexafuryl cyclotriphosphazene intermediate: respectively dissolving cyclotriphosphazene, an acid-binding agent and a furan derivative in a solvent A, and uniformly mixing; keeping the temperature of the solution of cyclotriphosphazene and the acid-binding agent at 50-130 ℃, then dropwise adding the furan derivative solution for 0.5-2 h, and continuously reacting for 6-24 h; and after the reaction is finished, washing and separating liquid, decompressing and rotary steaming, and drying at 60-120 ℃ for 4-24 hours to obtain the intermediate hexafuryl cyclotriphosphazene. Wherein the molar ratio of cyclotriphosphazene to furan compound is 1: 6-6.2, and the molar ratio of acid-binding agent to cyclotriphosphazene is 6-8.1: 1.

2) And (3) synthesis of a product: dissolving the hexafuryl cyclotriphosphazene intermediate and bismaleimide in a solvent B according to a certain proportion, uniformly mixing, reacting at 40-80 ℃ for 6-24 h, after the reaction is finished, performing suction filtration, washing with water, and drying at 50-100 ℃ for 6-24 h to obtain a product. The molar ratio of the intermediate to the bismaleimide is 1: 3-3.2.

In the step (1), the furan derivative is one of furfuryl amine, furfuryl alcohol and 5-hydroxymethyl furfural.

The solvent A in the step (1) is at least one of tetrahydrofuran, dimethyl sulfoxide, trichloromethane, benzene, toluene, xylene, N-dimethylformamide and N, N-dimethylacetamide.

The acid-binding agent in the step (1) is at least one of triethylamine, potassium carbonate and pyridine.

And (2) the reduced pressure rotary evaporation temperature in the step (1) is 30-70 ℃.

The intermediate structural formula in the step (1) is shown as a formula (1), a formula (2) and a formula (3).

The bismaleimide in the step (2) is at least one of 1, 2-bis (maleimide) ethane, 1, 4-bis (maleimide) butane, 1, 6-bis (maleimide) hexane, N '-1, 4-phenylenedimaleimide, N' -m-phenylenedimaleimide, N '-1, 2-phenylenedimaleimide, 4' -bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane.

And (3) the solvent B in the step (2) is at least one of tetrahydrofuran, dimethyl sulfoxide, trichloromethane, benzene, toluene, xylene, N-dimethylformamide and N, N-dimethylacetamide.

The flame retardant with the three-dimensional structure has the following beneficial effects:

(1) the synthetic method of the flame retardant with the three-dimensional structure is simple and easy to operate.

(2) The flame retardant with the three-dimensional structure provided by the invention is halogen-free, environment-friendly, efficient and broad-spectrum.

(3) The flame retardant with the three-dimensional structure can be used for polyvinyl acetate, polyethylene, polypropylene, polyolefin elastomer, polyurethane elastomer and the like, is compounded with ammonium polyphosphate for use, and has low addition and high flame retardant efficiency.

Drawings

FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of formula (1).

FIG. 2 is an infrared spectrum of the target product of formula (5).

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Those skilled in the art who have the benefit of this disclosure will appreciate that many non-essential modifications and adaptations to the present invention are possible and can still fall within the scope of the present invention.

Example 1:

synthesis of intermediates having the structure of formula (1): at room temperature, 0.03mol of hexachlorocyclotriphosphazene, 0.18mol of triethylamine and 80ml of toluene are added into a 250ml three-neck flask provided with a spherical condenser tube and a constant pressure dropping funnel and are uniformly mixed. 0.18mol of furfuryl amine are dissolved in 60ml of toluene in N₂Under protection, the mixture was added dropwise into a three-necked flask through a constant pressure separatory funnel and was drained after 1.5 hours. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (1). FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of formula (1).

Synthesis of the product formula (5): 0.06mol of N, N-m-phenylene bismaleimide and 300ml of tetrahydrofuran are added into a 500ml three-neck flask which is provided with a spherical condenser tube and a constant pressure dropping funnel at room temperature. 0.02mol of intermediate (1) is dissolved in 60ml of tetrahydrofuran under N₂Under protection, the mixture is slowly dripped into a three-neck flask through a constant-pressure separating funnel and is dripped out within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain light yellow solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product of formula (5). FIG. 2 is an infrared spectrum of the target product of formula (5).

Example 2:

synthesis of intermediates having the structure of formula (1): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of potassium carbonate and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfurylamine are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (1).

Synthesis of the product formula (5): at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain light yellow solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product of formula (5).

Example 3:

synthesis of intermediates having the structure of formula (1): at room temperature, 1mol of hexabromocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfurylamine are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (1).

Synthesis of product H-H: at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain light yellow solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product of formula (5).

Example 4:

synthesis of intermediates having the structure of formula (1): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfurylamine are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (1).

Synthesis of the product formula (6): at room temperature, 3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After dripping out, the bottle is openedThe temperature is increased to 60 ℃ and the reaction is stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain light yellow solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product of formula (6).

Example 5:

Synthesis of the product formula (6): at room temperature, 3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain light yellow solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product of formula (6).

Example 6:

synthesis of intermediates having the structure of formula (1): at room temperature, 1mol of hexabromocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfurylamine are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. After the reaction is finished, carrying out suction filtration, washing and separating liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquidAnd drying in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate formula (1).

Example 7:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (2).

Synthesis of the product formula (7): at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (7).

Example 8:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of potassium carbonate and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (2).

Example 9:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexabromocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (2).

Synthesis of the product formula (7): at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring for 1 hourAnd (4) dripping off. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (7).

Example 10:

Synthesis of the product formula (8): at room temperature, 3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (8).

Example 11:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of potassium carbonate and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. After the reaction is finished, carrying out suction filtration, washing and separating liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquidDrying the liquid in a vacuum oven at 120 ℃ for 12 hours to obtain an intermediate formula (2).

Example 12:

Example 13:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural are dissolved in 0.5L of toluene in N₂Under protection and mechanical stirringAnd dropwise adding the mixture into a reaction kettle, and completely dripping the mixture for 1.5 hours. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (3).

Synthesis of the product formula (9): at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (9).

Example 14:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of potassium carbonate and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (3).

Synthesis of the product formula (9): at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping under protection and mechanical stirringAdding into the reaction kettle, and dripping out in 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (9).

Example 15:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexabromocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (3).

Synthesis of product H-b: at room temperature, 3mol of N, N-m-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (9).

Example 16:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (3).

Synthesis of the product formula (10): at room temperature in the presence of cold3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle of the coagulation device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (10).

Example 17:

Synthesis of the product formula (10): at room temperature, 3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (10).

Example 18:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexabromocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural is dissolved in0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (3).

Synthesis of product (10): at room temperature, 3mol of 4,4' -bismaleimide diphenylmethane and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (10).

Example 19:

Synthesis of the product formula (11): at room temperature, 3mol of 2, 2-bis [4- (4-maleimide phenoxy) phenyl group is added into a 5L glass reaction kettle provided with a condensing device]Propane and 3L of tetrahydrofuran. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (11).

Example 20:

Synthesis of the product formula (12): at room temperature, 3mol of 2, 2-bis [4- (4-maleimide phenoxy) phenyl group is added into a 5L glass reaction kettle provided with a condensing device]Propane and 3L of tetrahydrofuran. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (12).

Example 21:

synthesis of an intermediate having the structure of formula (3): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of 5-hydroxymethylfurfural are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. After the reaction is finished, performing suction filtration, washing the separated liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying in a vacuum oven at 120 ℃ for 12 hours to obtain an intermediate body formula (3)。

Synthesis of the product formula (13): at room temperature, 3mol of 2, 2-bis [4- (4-maleimide phenoxy) phenyl group is added into a 5L glass reaction kettle provided with a condensing device]Propane and 3L of tetrahydrofuran. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (13).

Example 22:

Synthesis of the product formula (14): at room temperature, 3mol of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 3L of tetrahydrofuran were added in a 5L glass reaction kettle equipped with a condensing unit. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (14).

Example 23:

Synthesis of the product formula (15): at room temperature, 3mol of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 3L of tetrahydrofuran were added in a 5L glass reaction kettle equipped with a condensing unit. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (15).

Example 24:

Synthesis of the product formula (16): 5L glass with condensing device at room temperature3mol of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 3L of tetrahydrofuran are added into the reaction kettle. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (16).

Example 25:

Synthesis of the product formula (17): 3mol of N, N' -1, 4-phenylenedimaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device at room temperature. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (17).

Example 26:

intermediate with formula (2)The synthesis of (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (2).

Synthesis of the product formula (18): 3mol of N, N' -1, 4-phenylenedimaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device at room temperature. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (18).

Example 27:

Synthesis of the product formula (19): 3mol of N, N' -1, 4-phenylenedimaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device at room temperature. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (19).

Example 28:

Synthesis of the product formula (20): at room temperature, 3mol of N, N' -1, 2-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (20).

Example 29:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. Dissolving 6mol of furfuryl alcohol inIn 0.5L of toluene, in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (2).

Synthesis of the product formula (21): at room temperature, 3mol of N, N' -1, 2-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (21).

Example 30:

Synthesis of the product formula (22): at room temperature, 3mol of N, N' -1, 2-phenylene bismaleimide and 3L of tetrahydrofuran are added into a 5L glass reaction kettle provided with a condensing device. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering and filteringWashing with tetrahydrofuran and deionized water for 3 times to obtain solid powder, and drying in a vacuum oven at 60 deg.C for 20 hr to obtain the target product of formula (22).

Example 31:

Synthesis of the product formula (23): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (23).

Example 32:

synthesis of intermediates having the structure of formula (2): at room temperature, 1mol of hexachlorocyclotriphosphazene, 6mol of triethylamine and 2.5L of toluene are added into a 5L glass reaction kettle provided with a condensing device and are uniformly mixed. 6mol of furfuryl alcohol are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. The reaction is finishedAnd then carrying out suction filtration, washing and separating the solution for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain an intermediate compound formula (2).

Synthesis of the product formula (24): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (24).

Example 33:

Synthesis of the product formula (25): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (25).

Example 34:

Synthesis of the product formula (26): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (26).

Example 35:

Synthesis of the product formula (27): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (27).

Example 36:

Synthesis of the product formula (28): 3mol of 1, 2-bis (maleimide) ethane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (28).

Example 37:

Synthesis of the product formula (26): at room temperature, 3mol of 1, 4-bis (maleimido) butane and 3L of tetrahydrofuran were added in a 5L glass reaction vessel equipped with a condensing unit. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (26).

Example 38:

Synthesis of the product formula (27): at room temperature, 3mol of 1, 4-bis (maleimido) butane and 3L of tetrahydrofuran were added in a 5L glass reaction vessel equipped with a condensing unit. 1mol of intermediateDissolving formula (2) in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (27).

Example 39:

Synthesis of the product formula (28): at room temperature, 3mol of 1, 4-bis (maleimido) butane and 3L of tetrahydrofuran were added in a 5L glass reaction vessel equipped with a condensing unit. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (28).

Example 40:

synthesis of intermediates having the structure of formula (1): at room temperature, 1mol of hexachlorocyclotriphosphazene and 6m of hexachlorocyclotriphosphazene are added into a 5L glass reaction kettle provided with a condensing deviceThe ol triethylamine was mixed with 2.5L toluene. 6mol of furfurylamine are dissolved in 0.5L of toluene in N₂Under the protection and mechanical stirring, the mixture is dripped into a reaction kettle and dripped out after 1.5 h. After the dripping off, the temperature is raised to 120 ℃ and the reaction is continued to be stirred for 14 hours. And after the reaction is finished, carrying out suction filtration, washing and separating the liquid for 3-4 times, heating, decompressing, rotating and removing the solvent to obtain yellow oily liquid, and drying the yellow oily liquid in a vacuum oven at 120 ℃ for 12 hours to obtain the intermediate compound (1).

Synthesis of the product formula (29): 3mol of 1, 6-bis (maleimido) hexane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (1) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (29).

Example 41:

Synthesis of the product formula (30): 3mol of 1, 6-bis (maleimido) hexane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (2) is dissolved in 0.5L of tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After dripping off, the temperature is raised to 60 ℃ and stirring is continuedThe reaction is carried out for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (30).

Example 42:

Synthesis of the product formula (31): 3mol of 1, 6-bis (maleimido) hexane and 3L of tetrahydrofuran were added at room temperature in a 5L glass reactor equipped with a condensing unit. 1mol of the intermediate of formula (3) is dissolved in 0.5L tetrahydrofuran in N₂Slowly dropping into the reaction kettle under the protection and mechanical stirring, and completely dropping within 1 hour. After the dripping is finished, the temperature is raised to 60 ℃ and the reaction is continued to be stirred for 16 h. After the reaction is finished, filtering, washing tetrahydrofuran and deionized water for 3 times respectively to obtain solid powder, and drying in a vacuum oven at 60 ℃ for 20 hours to obtain the target product formula (31).

The application example is as follows:

the polymer, ammonium polyphosphate (APP) and the target product obtained by the invention are uniformly mixed (APP/product of the invention mass ratio is 3:1), and melt blending is performed according to the formula in table 1 to prepare the flame-retardant composite material. The flame retardant used in the comparative example was APP/Pentaerythritol (PER) (mass ratio 3: 1). And (3) carrying out a flame retardant property test according to GB/T2408 + 2008 standard, wherein the flame retardant property is shown in Table 1.

The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.

Claims

1. A three-dimensional structure flame retardant based on furan derivatives and cyclotriphosphazene is characterized in that the structural formula is shown as formula (4):

wherein-R₁-is-O-or-NH-; -R₂-is of

－R₃-is-H or-CHO.

2. The preparation method of the three-dimensional flame retardant based on the furan derivative and the cyclotriphosphazene is characterized by comprising the following steps:

1) synthesis of hexafuryl cyclotriphosphazene intermediate: respectively dissolving cyclotriphosphazene, an acid-binding agent and a furan derivative in a solvent A, and uniformly mixing; keeping the temperature of the solution of cyclotriphosphazene and the acid-binding agent at 50-130 ℃, then dropwise adding the furan derivative solution for 0.5-2 h, and continuously reacting for 6-24 h; after the reaction is finished, washing and separating liquid, decompressing and rotary steaming, and drying at 60-120 ℃ for 4-24 hours to obtain an intermediate hexafuryl cyclotriphosphazene;

the furan derivative in the step 1) is one of furfuryl amine, furfuryl alcohol and 5-hydroxymethyl furfural;

the structural formula of the intermediate hexafuryl cyclotriphosphazene in the step 1) is shown as a formula (1), a formula (2) or a formula (3):

2) and (3) synthesis of a product: dissolving a hexafuryl cyclotriphosphazene intermediate and bismaleimide in a solvent B in proportion, uniformly mixing, reacting at 40-80 ℃ for 6-24 h, and after the reaction is finished, performing suction filtration, washing with water, and drying at 50-100 ℃ for 6-24 h to obtain a product;

the bismaleimide in the step 2) is at least one of 1, 2-bis (maleimide) ethane, 1, 4-bis (maleimide) butane, 1, 6-bis (maleimide) hexane, N '-1, 4-phenylene bismaleimide, N' -m-phenylene bismaleimide, N '-1, 2-phenylene bismaleimide, 4' -bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane.

3. The method for preparing the three-dimensional structure flame retardant based on the furan derivative and the cyclotriphosphazene according to claim 2, wherein the molar ratio of the cyclotriphosphazene to the furan compound in the step 1) is 1: 6-6.2, and the molar ratio of the acid-binding agent to the cyclotriphosphazene is 6-8.1: 1.

4. The method for preparing the three-dimensional structure flame retardant based on the furan derivative and the cyclotriphosphazene according to claim 2, wherein the molar ratio of the intermediate in the step 1) to the bismaleimide is 1: 3-3.2.

5. The method for preparing three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene according to claim 2, wherein the solvent a of step 1) is at least one of tetrahydrofuran, dimethyl sulfoxide, chloroform, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide.

6. The method for preparing the three-dimensional flame retardant based on the furan derivative and the cyclotriphosphazene according to claim 2, wherein the acid-binding agent in the step 1) is at least one of triethylamine, potassium carbonate and pyridine.

7. The method for preparing the three-dimensional structure flame retardant based on the furan derivative and the cyclotriphosphazene according to claim 2, wherein the reduced pressure rotary evaporation temperature in the step 1) is 30-70 ℃.

8. The method for preparing three-dimensional structure flame retardant based on furan derivative and cyclotriphosphazene according to claim 2, wherein the solvent B in step 2) is at least one of tetrahydrofuran, dimethyl sulfoxide, chloroform, benzene, toluene, xylene, N-dimethylformamide, N-dimethylacetamide.