CN117126200A

CN117126200A - Phosphorus imide-containing alicyclic epoxy molecule and preparation method thereof

Info

Publication number: CN117126200A
Application number: CN202310905841.6A
Authority: CN
Inventors: 蒋之铭; 李红颜
Original assignee: Qingdao University
Current assignee: Qingdao University
Priority date: 2023-07-24
Filing date: 2023-07-24
Publication date: 2023-11-28

Abstract

The invention discloses a phosphorus imide-containing alicyclic epoxy molecule, which relates to the technical field of flame retardant materials and has the structural formula:wherein R is-C ₆ H ₅ or-OC ₆ H ₅ M is 0 or 1, n is 2, 3, 4, 5 or 6. Also discloses a preparation method of the phosphorus imide type alicyclic epoxy molecule, which comprises the following steps: reacting double bond-containing anhydride with an alcohol amine compound to obtain an intermediate 1; the intermediate 1 and the chlorophosphoryl compound undergo substitution reaction to obtain an intermediate 2; and (3) performing epoxidation reaction on the intermediate 2 and an oxidant to obtain the phosphorus imide type alicyclic epoxy molecule. The phosphorus-containing imide type alicyclic epoxy molecule has a phosphorus-containing group and an imide structure, so that a cured product of the phosphorus-containing imide type alicyclic epoxy molecule has excellent flame retardant property, and the limiting oxygen index can reach more than 35%.

Description

Phosphorus imide-containing alicyclic epoxy molecule and preparation method thereof

Technical Field

The invention relates to the technical field of flame retardant materials, in particular to a phosphorus imide-containing alicyclic epoxy molecule and a preparation method thereof.

Background

Epoxy resin is a thermosetting polymer material which is generally characterized by containing two or more epoxy groups, taking aliphatic, alicyclic or aromatic organic compounds as a framework, and forming a three-dimensional cross-linked network through epoxy group reaction, and has been widely applied to the fields of electronic information, aerospace, wind power generation, transportation, deep sea diving and the like because of excellent physical, chemical properties, wettability, adhesiveness, oil resistance, water resistance, corrosion resistance and insulation. Compared with the glycidyl ether type epoxy resin, the alicyclic epoxy resin is obtained by the epoxidation reaction of unsaturated alicyclic compounds through organic peroxy acid, so that the content of free chlorine or metal ions is low, and the condensate has lower dielectric constant and dielectric loss. In addition, alicyclic epoxy resin does not contain strong ultraviolet chromophores such as aromatic rings, and the like, and is decomposed to generate small molecular volatile matters such as carbon dioxide, carbon monoxide, water and the like when being exposed to a high-voltage arc, and free carbon is not generated to form a conductive path, so that the alicyclic epoxy resin has excellent high-voltage leakage resistance. However, the limiting oxygen index of the alicyclic epoxy resin is only about 20%, the alicyclic epoxy resin is extremely easy to burn, and the requirements of the fields of electronics, transportation and the like on fire safety materials cannot be met.

The preparation of the flame-retardant epoxy resin mainly adopts two modes of an additive type and a reaction type, wherein the additive type flame retardance is rapid and simple, but the flame retardant is introduced by adopting a physical blending mode, so that the problems of poor compatibility, easy precipitation, mechanical property deterioration and the like are easy to occur, and the use and development of the flame-retardant epoxy resin are limited; the reactive flame retardation can reduce the risk of deterioration of physical properties of the material, so that the curing system can obtain excellent flame retardation and thermal stability, and can also maintain the performance advantage of the material. In the research of the prior reactive flame-retardant alicyclic epoxy resin, the problem of poor flame retardant performance exists, and the requirement of high fire safety cannot be met.

Therefore, in order to solve the above problems, it is needed to study a flame-retardant epoxy resin, and to greatly improve the flame-retardant performance of the cured epoxy resin, and simultaneously, to meet the requirements of low dielectric properties in the fields of high frequency, high speed and communication through molecular structure design.

Disclosure of Invention

In order to solve the technical problems, the invention discloses a phosphorus-containing imide type alicyclic epoxy molecule and a preparation method thereof, wherein a phosphorus-containing group and an imide structure are simultaneously introduced on the basis of the alicyclic epoxy molecule, and the molecule has the phosphorus-containing group, the imide structure and the epoxy group, so that a condensate of the phosphorus-containing imide type alicyclic epoxy molecule has excellent flame retardant property and dielectric property, and meets the performance requirements of the electronic packaging material in the fields of high-frequency and high-speed communication.

In order to achieve the above purpose, the present invention adopts the following technical scheme:

the first aspect of the invention provides a phosphorus imide-containing alicyclic epoxy molecule, which has the structural formula:

molecular formula C _2m+2n+16 H _4n+16 O ₉ PR, wherein R is-C ₆ H ₅ or-OC ₆ H ₅ M is 0 or 1, n is 2, 3, 4, 5 or 6.

The second aspect of the invention provides a preparation method of the phosphorus imide-containing alicyclic epoxy molecule, which comprises the following steps:

s1, reacting double bond-containing anhydride with an alcohol amine compound to obtain an intermediate 1;

s2, carrying out substitution reaction on the intermediate 1 and a chlorophosphoryl compound to obtain an intermediate 2;

and S3, performing epoxidation reaction on the intermediate 2 and an oxidant to obtain the phosphorus imide type alicyclic epoxy molecule.

Optionally, in step S1, the double bond-containing anhydride is reacted with an alcohol amine compound to obtain an intermediate 1, which specifically includes: and (2) mixing double bond-containing anhydride with an alcohol amine compound, reacting under the condition of solvent or no solvent, wherein the reaction temperature is 120-140 ℃, the reaction time is 3-6 h, and extracting after the reaction is finished to obtain the intermediate 1.

Optionally, in step S1, the double bond-containing anhydride is nadic anhydride or tetrahydrophthalic anhydride, the alcohol amine compound is ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol or 6-amino-1-hexanol, and the molar ratio of the anhydride to the alcohol amine compound is 1:1-1:1.1.

Optionally, in step S1, when the reaction is performed in the presence of a solvent, the solvent is toluene, a catalyst is added, after the reaction is completed, toluene is removed by reduced pressure distillation to obtain a crude product, and the crude product is dissolved in dichloromethane and extracted; when the reaction is carried out under the condition of no solvent, a crude product is obtained after the reaction is finished, and the crude product is dissolved by methylene dichloride and then extracted.

Optionally, the catalyst is triethylamine.

Alternatively, in step S1, the solution used for extraction is a 0.5% w/w hydrochloric acid solution, a 1% w/w sodium carbonate solution, a saturated sodium chloride solution in this order. Wherein, hydrochloric acid solution is used for removing unreacted alcohol amine compound and catalyst triethylamine, sodium carbonate solution is used for removing hydrochloric acid, and saturated sodium chloride solution is used for removing sodium carbonate and drying.

Optionally, in step S2, the step of performing a substitution reaction between the intermediate 1 and the chlorophosphoryl compound specifically includes:

dropwise adding the chlorophosphoryl compound into the mixed solution containing the intermediate 1 and the acid binding agent at the temperature of 0-5 ℃, reacting for 12-24 h at the temperature of 0-40 ℃ after the dropwise adding, and extracting to obtain the intermediate 2.

Optionally, in step S2, the solvent is dichloromethane, the chlorophosphoryl compound is any one of phenyl dichlorophosphate or phenyl phosphoryl dichloride, the acid-binding agent is triethylamine or pyridine, the molar ratio of the intermediate 1 to the chlorophosphoryl compound is 3:1-2:1, and the molar ratio of the acid-binding agent to the chlorophosphoryl compound is 3:1-2:1; the solutions used for the extraction were, in order, 0.5% w/w hydrochloric acid solution, 1% w/w sodium carbonate solution and saturated sodium chloride solution. Wherein, hydrochloric acid solution is used for removing triethylamine, sodium carbonate solution is used for removing unreacted phenyl dichlorophosphate or phenyl phosphoryl dichloride and hydrochloric acid, and saturated sodium chloride solution is used for removing sodium carbonate and has the function of drying.

Optionally, in step S3, the step of performing an epoxidation reaction between the intermediate 2 and the oxidizing agent specifically includes:

dropwise adding the dissolved intermediate 2 into a solution dissolved with an oxidant at 0-5 ℃, reacting for 8-24 hours at 0-25 ℃, and quenching and extracting by a reducing agent to obtain the phosphorus imide type alicyclic epoxy molecule.

Optionally, in step S3, the solvent is dichloromethane, the oxidant is m-chloroperoxybenzoic acid, the reducing agent is sodium bisulphite, sodium sulfite or sodium thiosulfate, and the molar ratio of the intermediate 2 to the oxidant is 1:2-1:5; the solution used for extraction was in turn a 1% w/w sodium carbonate solution, saturated sodium chloride solution.

The invention has the advantages that,

(1) The phosphorus-containing imide type alicyclic epoxy molecule has a phosphorus-containing group and an imide structure, and by means of the catalytic carbonizing effect of the phosphorus-containing group and an expansion carbon layer formed by the phosphorus-containing group and the imide structure, heat and oxygen transfer in the combustion process can be effectively retarded, so that a condensate of the phosphorus-containing imide type alicyclic epoxy molecule has excellent flame retardant performance, and the Limiting Oxygen Index (LOI) can reach more than 35%.

(2) The alicyclic epoxy molecule is obtained through double bond oxidation, epoxy chloropropane is not used, byproducts such as chloride ions and sodium ions are not contained, the alicyclic epoxy molecule has lower dielectric constant and dielectric loss, the dielectric constant and dielectric loss can be further reduced through combination with a low-dielectric imide structure, and the alicyclic epoxy molecule has good application prospect in the fields of high-frequency and high-speed communication.

(3) The phosphorus imide type alicyclic epoxy molecule is obtained through a synthesis method, no special equipment or special reagent is used, and the intermediate and the final product can be effectively purified through a simple extraction procedure, so that the phosphorus imide type alicyclic epoxy molecule has higher yield.

Drawings

FIG. 1 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule of the present invention;

FIG. 2 is a nuclear magnetic resonance spectrum of a phosphorus imide type alicyclic epoxy molecule shown in example 1 of the present invention, wherein a is hydrogen spectrum [ ] ¹ H-NMR), b is phosphorus spectrum [ ] ³¹ P-NMR)；

FIG. 3 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 1 of the present invention;

FIG. 4 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 2 of the present invention;

FIG. 5 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 3 of the present invention;

FIG. 6 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 4 of the present invention;

FIG. 7 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 5 of the present invention;

FIG. 8 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 6 of the present invention;

FIG. 9 is a block diagram of a phosphorus imide-containing cycloaliphatic epoxy molecule shown in example 7 of the present invention;

FIG. 10 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 8 of the present invention;

FIG. 11 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 9 of the present invention;

FIG. 12 is a block diagram of a phosphorus imide containing cycloaliphatic epoxy molecule shown in example 10 of the present invention;

FIG. 13 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 11 of the present invention;

FIG. 14 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 12 of the present invention;

FIG. 15 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 13 of the present invention;

FIG. 16 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule containing structure shown in example 14 of the present invention;

FIG. 17 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 15 of the present invention;

FIG. 18 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule containing structure shown in example 16 of the present invention;

FIG. 19 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule containing structure shown in example 17 of the present invention;

FIG. 20 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 18 of the present invention;

FIG. 21 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule containing structure of example 19 of the present invention;

FIG. 22 is a block diagram showing a phosphorus imide type alicyclic epoxy molecule in example 20 of the present invention.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

A phosphorus imide-containing alicyclic epoxy molecule has a structural formula shown in figure 1, wherein R is-C ₆ H ₅ or-OC ₆ H ₅ M is 0 or 1, n is 2, 3, 4, 5 or 6.

The preparation method of the phosphorus imide-containing alicyclic epoxy molecule comprises the following steps:

step S1, mixing double bond-containing anhydride with an alcohol amine compound, and then reacting under the condition of solvent or no solvent, wherein the reaction temperature is 120-140 ℃, the reaction time is 3-6 h, and extracting after the reaction is finished to obtain an intermediate 1;

step S2, dropwise adding a chlorophosphoryl compound into a mixed solution containing the intermediate 1 and an acid binding agent at the temperature of 0-5 ℃, reacting for 12-24 hours at the temperature of 0-40 ℃ after the dropwise adding, and extracting to obtain an intermediate 2;

Step S3, dropwise adding the dissolved intermediate 2 into a solution dissolved with an oxidant at the temperature of 0-5 ℃, reacting for 8-24 hours at the temperature of 0-25 ℃, and quenching and extracting by a reducing agent to obtain the phosphorus imide-containing alicyclic epoxy molecule.

The invention is further illustrated by the following examples:

example 1

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 3.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 12.46g of ethanolamine, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with dichloromethane, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 78.7%.

Step S2, adding 32.36g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 14.98g of phenyl dichlorophosphate into an ice bath, cooling to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 86.6%.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 32.84g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 87.2%.

By passing through ¹ H-NMR ³¹ The final product synthesized in example 1 was characterized by P-NMR as shown in FIGS. 2 a and b, respectively. Wherein, ¹ 1.01 to 1.32ppm of 4H in H-NMR are assigned to-CH on cyclohexane ring ₂ 2.80 to 2.85ppm of 4H's belonging to the proton of the-CH-group attached to the methylene group on the cyclohexane ring, 2.99 to 3.01ppm of 4H's belonging to the proton of the-CH-group on the epoxy structure, 3.17 to 3.21ppm of 4H's belonging to the proton of the-CH-group attached to the cyclohexane ring and the imide ring, 3.58 to 3.62ppm of 4H's belonging to the-CH-group adjacent to the imide ring ₂ Protons of 4.07 to 4.15ppm of 4H are assigned to the-CH close to the phosphate structure ₂ Hydrogen atoms, 7.09 to 7.38ppm of 5H groupsProtons on the benzene ring. ³¹ The only characteristic peak in P-NMR is attributed to the phosphorus atom on the phosphate structure.

Example 2

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 4.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 16.52g of 3-amino-1-propanol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 76.5%. The mole ratio of nadic anhydride to 3-amino-1-propanol was 1:1.1.

Step S2, adding 34.55g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 14.99g of phenyl dichlorophosphate into an ice bath, cooling to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 84.2%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 34.51g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.6%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 3

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 5.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 19.61g of 4-amino-1-butanol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 74.6%. The mole ratio of nadic anhydride to 4-amino-1-butanol was 1:1.1.

Step S2, adding 36.74g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 14.99g of phenyl dichlorophosphate into an ice bath, cooling to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 82.5%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 36.18g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 81.4%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 4

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 6.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 22.70g of 5-amino-1-amyl alcohol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, sodium carbonate solution and saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain an intermediate 1, wherein the yield is 73. The mole ratio of nadic anhydride to 5-amino-1-pentanol was 1:1.1.

Step S2, 38.93g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 14.99g of phenyl dichlorophosphate is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 81.6%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution containing 37.85g of intermediate 2 into an ice bath, cooling to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 80.7%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 5

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 7.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 25.79g of 6-amino-1-hexanol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 71.4%. The molar ratio of nadic anhydride to 6-amino-1-hexanol was 1:1.1.

Step S2, 41.12g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 14.99g of phenyl dichlorophosphate is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 80.4%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 39.52g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.3%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 6

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 8.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 12.46g of ethanolamine, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with dichloromethane, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 78.7%. The mole ratio of nadic anhydride to ethanolamine is 1:1.02.

Step S2, adding 32.36g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 13.85g of phenyl phosphoryl dichloride into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 87.5%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 31.86g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.9%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 7

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 9.

The preparation method comprises the following steps:

Step S2, adding 34.55g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 13.85g of phenyl phosphoryl dichloride into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 82.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 33.52g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, cooling to room temperature after dropwise adding, reacting for 24 hours, filtering after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain a final product with the yield of 78.6%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 8

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 10.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 19.61g of 4-amino-1-butanol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 74.6%. The mole ratio of nadic anhydride to 4-amino-1-butanol was 1:1.1.

Step S2, adding 36.74g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 13.85g of phenyl phosphoryl dichloride into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 81.2%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 35.19g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, cooling to room temperature after dropwise adding, reacting for 24 hours, filtering after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain a final product with the yield of 83.2%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 9

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 11.

The preparation method comprises the following steps:

Step S2, 38.93g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 13.85g of phenyl phosphoryl dichloride is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 85.2%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 36.85g of intermediate 2 is dissolved into an ice bath, heating to room temperature after dropwise adding, reacting for 24 hours, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 86.7%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 10

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 12.

The preparation method comprises the following steps:

step S1, adding 32.83g of nadic anhydride, 25.79g of 6-amino-1-hexanol, 14.77g of triethylamine and 100mL of toluene into a three-neck flask with a condenser tube, a thermometer and a stirrer, heating to 120 ℃, reacting for 4 hours, removing toluene through reduced pressure distillation after the reaction is finished to obtain a crude product, dissolving the crude product with methylene dichloride, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 71.4%. The molar ratio of nadic anhydride to 6-amino-1-hexanol was 1:1.1.

Step S2, 41.12g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 13.85g of phenyl phosphoryl dichloride is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 85.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 38.51g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, cooling to room temperature after dropwise adding, reacting for 24 hours, filtering after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain a final product with the yield of 79.5%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 11

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 13.

The preparation method comprises the following steps:

step S1, adding 30.43g of tetrahydrophthalic anhydride and 12.83g of ethanolamine into a three-neck flask with a thermometer and a stirrer, heating to 130 ℃, reacting for 4 hours under the condition of no solvent, dissolving a crude product with dichloromethane after the reaction is finished, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 75.8%. The molar ratio of tetrahydrophthalic anhydride to ethanolamine is 1:1.05.

Step S2, adding 30.46g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 14.98g of phenyl dichlorophosphate into an ice bath, cooling to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 84.9%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S2, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 31.39g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 78. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 12

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 14.

The preparation method comprises the following steps:

step S1, adding 30.43g of tetrahydrophthalic anhydride and 16.52g of 3-amino-1-propanol into a three-neck flask with a thermometer and a stirrer, heating to 130 ℃, reacting for 4 hours under the condition of no solvent, dissolving a crude product with dichloromethane after the reaction is finished, respectively extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 74.6%. The molar ratio of tetrahydrophthalic anhydride to 3-amino-1-propanol was 1:1.05.

Step S2, adding 34.82g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 14.99g of phenyl dichlorophosphate into an ice bath, cooling to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 85.4%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 33.06g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.6%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 13

The structural formula of the phosphorus imide-containing alicyclic epoxy molecule is shown in fig. 15.

The preparation method comprises the following steps:

step S1, adding 30.43g of tetrahydrophthalic anhydride and 19.61g of 4-amino-1-butanol into a three-neck flask with a thermometer and a stirrer, heating to 130 ℃, reacting for 4 hours under the condition of no solvent, dissolving a crude product with dichloromethane after the reaction is finished, respectively extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 73.4%. The molar ratio of tetrahydrophthalic anhydride to 4-amino-1-butanol was 1:1.05.

Step S2, 39.19g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 14.99g of phenyl dichlorophosphate is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 84 degrees. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 34.72g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 83.5%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 14

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 16.

The preparation method comprises the following steps:

step S1, adding 30.43g of tetrahydrophthalic anhydride and 22.70g of 5-amino-1-pentanol into a three-neck flask with a thermometer and a stirrer, heating to 130 ℃, reacting for 4 hours under the condition of no solvent, dissolving a crude product with dichloromethane after the reaction is finished, respectively extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 73.4%. The molar ratio of tetrahydrophthalic anhydride to 5-amino-1-pentanol was 1:1.05.

Step S2, adding 43.56g of the intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask with a condenser, a thermometer and a stirrer, dropwise adding 14.99g of phenyl dichlorophosphate into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain the intermediate 2 with the yield of 82. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of methylene dichloride into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 36.38g of methylene dichloride solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 80.7%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 15

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 17.

The preparation method comprises the following steps:

step S1, adding 30.43g of tetrahydrophthalic anhydride and 25.79g of 6-amino-1-hexanol into a three-neck flask with a thermometer and a stirrer, heating to 130 ℃, reacting for 4 hours under the condition of no solvent, dissolving a crude product with dichloromethane after the reaction is finished, extracting and purifying with 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively, and distilling an organic phase under reduced pressure to obtain an intermediate 1 with the yield of 71.5%. The molar ratio of tetrahydrophthalic anhydride to 6-amino-1-hexanol was 1:1.05.

Step S2, 47.93g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 14.99g of phenyl dichlorophosphate is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 80.4%. The molar ratio of the intermediate 1, the phenyl dichlorophosphate and the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution containing 39.52g of intermediate 2 into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.3%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 16

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 18.

The preparation method comprises the following steps:

Step S2, adding 30.46g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 13.85g of phenyl phosphoryl dichloride into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 85.9%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 30.44g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 80.4%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 17

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 19.

The preparation method comprises the following steps:

Step S2, 34.82g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 13.85g of phenyl phosphoryl dichloride is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 86.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution in which 32.11g of intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 81.2%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 18

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 20.

The preparation method comprises the following steps:

Step S2, 39.19g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 13.85g of phenyl phosphoryl dichloride is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 85.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 33.77g of dichloromethane solution in which the intermediate 2 is dissolved into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 81.3%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 19

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in figure 21.

The preparation method comprises the following steps:

Step S2, adding 43.56g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding 13.85g of phenyl phosphoryl dichloride into an ice bath, heating to room temperature after the dropwise addition, reacting for 12 hours, extracting and purifying by using a 0.5% hydrochloric acid solution, a 1% sodium carbonate solution and a saturated sodium chloride solution respectively after the reaction is finished, and distilling an organic phase under reduced pressure to obtain intermediate 2 with the yield of 81.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution containing 35.43g of intermediate 2 into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 80.5%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

Example 20

The structural formula of the phosphorus imide type alicyclic epoxy molecule is shown in fig. 22.

The preparation method comprises the following steps:

Step S2, 47.93g of intermediate 1, 15.80g of triethylamine and 200mL of dichloromethane are added into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, 13.85g of phenyl phosphoryl dichloride is dropwise added into an ice bath, the mixture is cooled to room temperature after the dropwise addition, the reaction is carried out for 12 hours, after the reaction is finished, 0.5% hydrochloric acid solution, 1% sodium carbonate solution and saturated sodium chloride solution are respectively used for extraction and purification, and an organic phase is distilled under reduced pressure to obtain intermediate 2 with the yield of 80.4%. The molar ratio of the intermediate 1 to the phenyl phosphoryl dichloride to the triethylamine is 2.2:1:2.2.

Step S3, adding 36.20g of m-chloroperoxybenzoic acid (the mass fraction is 85%) and 300mL of dichloromethane into a three-neck flask provided with a condenser tube, a thermometer and a stirrer, dropwise adding a dichloromethane solution containing 37.10g of intermediate 2 into an ice bath, reacting for 12 hours in the ice bath after the dropwise adding, carrying out suction filtration after the reaction is finished, dropwise adding filtrate into a saturated sodium bisulfite solution at 0-5 ℃ for quenching, extracting with a 1% sodium carbonate solution and a saturated sodium chloride solution respectively, and carrying out reduced pressure distillation on an organic phase to obtain a final product with the yield of 85.3%. The molar ratio of the intermediate 2 to the m-chloroperoxybenzoic acid is 1:3.

It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.

Claims

1. A phosphorus imide-containing alicyclic epoxy molecule is characterized in that the structural formula is as follows:

wherein R is-C ₆ H ₅ or-OC ₆ H ₅ M is 0 or 1, n is 2, 3, 4, 5 or 6.

2. A method for preparing the phosphorus imide-containing cycloaliphatic epoxy molecule as claimed in claim 1, comprising the steps of:

3. A process for the preparation of a phosphorus imide containing cycloaliphatic epoxy molecule as claimed in claim 2, wherein,

in the step S1, the double bond-containing anhydride reacts with an alcohol amine compound to obtain an intermediate 1, which specifically comprises the following steps: and (2) mixing double bond-containing anhydride with an alcohol amine compound, reacting under the condition of solvent or no solvent, wherein the reaction temperature is 120-140 ℃, the reaction time is 3-6 h, and extracting after the reaction is finished to obtain the intermediate 1.

4. The method for producing a phosphorus imide type alicyclic epoxy molecule according to claim 2, wherein in the step S1, the double bond containing acid anhydride is nadic acid anhydride or tetrahydrophthalic acid anhydride, the alcohol amine compound is ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol or 6-amino-1-hexanol, and the molar ratio of the acid anhydride to the alcohol amine compound is 1:1 to 1:1.1.

5. The method for producing a phosphorus imide-containing alicyclic epoxy molecule as claimed in claim 2, wherein in step S1, when the reaction is carried out in the presence of a solvent, the solvent is toluene, and a catalyst is added, and after the reaction is completed, toluene is removed by distillation under reduced pressure to obtain a crude product, and the crude product is dissolved with methylene chloride and then extracted; when the reaction is carried out under the condition of no solvent, a crude product is obtained after the reaction is finished, and the crude product is dissolved by methylene dichloride and then extracted.

6. A process for the preparation of a phosphorus imide containing cycloaliphatic epoxy molecule as claimed in claim 3, wherein in step S1, the extraction is performed using a solution of 0.5% w/w hydrochloric acid, 1% w/w sodium carbonate and saturated sodium chloride in this order.

7. The method for preparing a phosphorus imide containing alicyclic epoxy molecule as claimed in claim 2, wherein in the step S2, the step of performing substitution reaction between the intermediate 1 and the chlorophosphoryl compound specifically comprises:

8. The method for producing a phosphorus imide containing cycloaliphatic epoxy molecule of claim 7,

in the step S2, the solvent is dichloromethane, the chlorophosphoryl compound is any one of phenyl dichlorophosphate or phenyl phosphoryl dichloride, the acid-binding agent is triethylamine, the mol ratio of the intermediate 1 to the chlorophosphoryl compound is 3:1-2:1, and the mol ratio of the acid-binding agent to the chlorophosphoryl compound is 3:1-2:1; the solutions used for the extraction were, in order, 0.5% w/w hydrochloric acid solution, 1% w/w sodium carbonate solution and saturated sodium chloride solution.

9. A process for the preparation of a phosphorus imide containing cycloaliphatic epoxy molecule as claimed in claim 2, wherein,

in step S3, the step of performing an epoxidation reaction between the intermediate 2 and the oxidizing agent specifically includes:

Dropwise adding the dissolved intermediate 2 into a solution dissolved with an oxidant at 0-5 ℃, reacting for 8-24 hours at 0-25 ℃, and quenching and extracting by a reducing agent to obtain the phosphorus imide-containing alicyclic epoxy molecule.

10. The method for producing a phosphorus imide containing cycloaliphatic epoxy molecule as claimed in claim 9, wherein,

in the step S3, the solvent is dichloromethane, the oxidant is m-chloroperoxybenzoic acid, the reducing agent is sodium bisulphite, sodium sulfite or sodium thiosulfate, and the molar ratio of the intermediate 2 to the oxidant is 1:2-1:5; the solution used for extraction was in turn a 1% w/w sodium carbonate solution, saturated sodium chloride solution.