CN103288845B - Spiro-compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane and synthetic method thereof - Google Patents

Abstract

The invention relates to a spiro-compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane. The molecular formula of the 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane is C9H8O6, and the structural formula is shown in the specification. The 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane disclosed by the invention is a highly symmetric oxygenous polybasic spiro-compound; according to the invention, the 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5] hendecane generates a linear polymer by realizing the ring-opening polymerization initiated through an initiating agent under a certain condition by being used as a curing agent in epoxide resin and generates volume expansion reaction, so that the epoxide resin is subjected to volume expansion caused by no volume shrinkage in a curing process.

Description

Spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane and its synthesis method

technical field

The invention relates to a spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane and a synthesis method thereof.

Background technique

Thermosetting epoxy resins will shrink in volume during the curing process, which will cause the strength of the material to decrease, and even cause defects such as micro-cracks or cracks, dimensional instability, or degumming of the transfer joints. Common methods to reduce the volume shrinkage of epoxy resins include: reducing the content of active functional groups in the reaction system; selecting a curing system with a lower reaction temperature; adding inorganic powder fillers; toughening modification, etc. However, these methods have their own shortcomings and application limitations, such as not being able to significantly improve the volume shrinkage of the epoxy resin system; increasing the viscosity of the reaction system, resulting in bubbles that are difficult to eliminate; high cost and difficult to realize industrial production.

The emergence of expansion monomers fundamentally solves the problem of volume shrinkage of epoxy resin systems. So far, the expansion monomers that have been found are only limited to compounds with structures such as bicyclic orthoesters, spirocyclic orthoesters and spirocyclic orthocarbonates. Among them, the volume expansion rate of the spiro ring orthocarbonate is more ideal when it is polymerized.

At present, scholars mainly add expansion monomers such as 3,9-bis(2-norbornene)-1,5,7,11-tetraoxaspiro[5,5]undecane, 3,9-bis(p-methoxybenzylidene)-1,5,7,11-tetraoxaspiro[5,5]undecane and other research ideas related to the curing shrinkage of epoxy resin , but these studies are still limited to the laboratory stage, the cost of material development is high, and the practical application is limited.

Contents of the invention

The technical problem to be solved by the present invention is to provide a spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecyl for the above-mentioned deficiencies in the prior art The alkane and its synthesis method have the advantages of simple operation, mild conditions, and easy realization of industrial production.

The technical scheme that the present invention adopts for solving the above-mentioned problem is:

The spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane has a molecular formula of C ₉ H ₈ O ₆ and a structural formula of

The synthetic method of above-mentioned spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane is divided into three steps: (1) by polyhalogenated hydrocarbon 1 , 3-dibromo-2,2-bis(bromomethyl)propane uses water as solvent, under the action of nitrilation agent, synthesizes 1,3-dinitrile- 2,2-bis(nitrilemethyl)propane;

(2) 1,3-dicarboxy-2,2-bis(nitrilemethyl)propane is hydrolyzed under the action of strong inorganic acid to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane.

(3) The exchange reaction of 1,3-dicarboxy-2,2-di(acetoxy)propane and acetic anhydride under the action of a catalyst produces the symmetrical product 2,4,8,10-tetracarbonyl-3,9-di Oxaspiro[5,5]undecane.

According to the above scheme, the molar ratio of the solvent water to the ligand-free copper catalyst is 5:1˜7:1.

According to the above scheme, the nitrilation agent is anhydrous K ₄ Fe(CN) ₆ , anhydrous K ₄ Fe(CN) ₆ and polyhalogenated hydrocarbon 1,3-dibromo-2,2-bis(bromomethyl ) The molar ratio of propane is 3:2 to 5:4.

According to the above scheme, the phase transfer catalyst is tetrabutylammonium bromide (TBAB), and the ligand-free copper catalyst is Cu(OAc)2.

According to the above scheme, the molar ratio of the phase transfer catalyst TBAB to the polyhalogenated hydrocarbon 1,3-dibromo-2,2-bis(bromomethyl)propane is 1:1～1:1.5, and the copper without ligand The catalyst Cu(OAc) ₂ accounts for 8%-10% of the total mass of the phase transfer catalyst.

According to the above scheme, the reaction temperature of the step (1) is 160° C. to 200° C., and the reaction time is 50 to 80 minutes.

According to the above scheme, the hydrolysis step reacts 1,3-dicyano-2,2-bis(nitrile methyl)propane with water in the presence of strong inorganic acid, and the amount of the hydrolysis reaction water is the same as that of 1,3 - The molar ratio of dinitrile-2,2-bis(nitrilemethyl)propane is 1:1.5˜1:2.0.

According to the above scheme, the strong inorganic acid is 98% concentrated sulfuric acid, and the molar ratio of concentrated sulfuric acid to 1,3-dicyano-2,2-bis(nitrile methyl)propane is 1:1˜1.5:1.

According to the scheme above, the catalyst in the step (3) is glacial acetic acid, and the catalyst is 0.1 to 0.15 times the molar amount of the reactant 1,3-dicarboxy-2,2-bis(acetoxy)propane.

According to the scheme above, the molar ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane to acetic anhydride in the step (3) is 1:1.5-2.1.

According to the above scheme, the reaction temperature in the step (3) is 90-110° C., and the reaction time is 6-12 hours.

The synthesis method of the above-mentioned spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane, the specific steps are as follows:

(1) According to the molar ratio of 3:2 to 5:4, prepare the anhydrous K ₄ Fe(CN) ₆ and 1,3-dibromo-2,2-bis(bromomethyl)propane as the nitrilation agent for later use; The molar ratio of transfer catalyst TBAB to 1,3-dibromo-2,2-bis(bromomethyl)propane is 1:1～1:1.5 to prepare TBAB; ligand-free copper catalyst Cu(OAc) ₂ occupies the phase transfer 8% to 10% of the total mass of the catalyst; according to the molar ratio of the amount of solvent water to the copper catalyst being 5:1 to 7:1, water is taken for later use.

Add Cu(OAc) ₂ catalyst to solvent water, stir until homogeneous, then add anhydrous K ₄ [Fe(CN) ₆ ], TBAB and 1,3-dibromo-2,2-bis(bromomethyl) Propane, seal the container and heat the reaction at 160°C to 200°C for 50min to 80min. After the reaction, let the system cool down to room temperature naturally, extract the product with ether three times, use a rotary evaporator to rotate the ether, GC detection and analysis, and make the product 1,3-dicyano-2,2-bis(nitrile methyl)propane is purified by chromatographic column;

(2) Under a nitrogen atmosphere, add 2/3 of the total volume of required water to a reactor equipped with a stirrer at room temperature (the total amount of required water and 1,3-dinitrile-2,2- The molar ratio of bis(nitrile methyl)propane is 1:1.5～1:2.0); then pour 98% H ₂ SO ₄ , sulfuric acid and 1,3-dicyano-2,2-bis(nitrile methyl)propane The molar ratio is 1:1~1.5:1, the temperature of the reaction system is raised to 120°C, and then the 1,3-dicyano-2,2-bis(nitrile methyl)propane prepared in the above steps is introduced within 1h , the temperature of the reaction system is controlled at 120°C, and then kept at this temperature for 20 to 40 minutes, then add the remaining 1/3 of the total volume of water required within 10 minutes, and raise the temperature to 130°C for 6 hours, stop after the reaction is over Stirring, the reaction medium is layered, allowed to cool naturally to 90°C, and the upper layer and the lower layer are separated to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane;

(3) According to the molar ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane and acetic anhydride is 1:1.5～2.1, the catalyst glacial acetic acid is 1,3-dicarboxy-2,2- 0.1 to 0.15 times the molar amount of bis(acetoxy)propane, put 1,3-dicarboxy-2,2-bis(acetoxy)propane, acetic anhydride and glacial acetic acid in a place with agitator, reflux condenser and In the three-necked flask with a thermometer, the reaction temperature is controlled at 90-110°C, and the reaction time is 6-12 hours until the reaction liquid is clarified and the reaction is completed; stop heating after the reaction is completed, and the product is distilled under reduced pressure, and the residue is reconstituted with chloroform. Crystallize, filter, dry and weigh to obtain 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane.

The reaction process of the present invention is as follows:

Compared with the prior art, the present invention has the advantages of:

First, 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane is a highly symmetrical oxygen-containing multi-component spiro compound, which is used in epoxy resin As a curing agent, under certain conditions, the ring-opening polymerization is initiated by the initiator to form a linear polymer, and a volume expansion reaction occurs, so that the volume of the epoxy resin does not shrink or expand during the curing process. The present invention develops 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane with expansion effect from the acid anhydride curing agent, the method is simple and easy, and the conditions Mild, the product is pure, and the yield can reach 96.2% to 98.5%.

Second, the present invention uses polyhalogenated hydrocarbon 1,3-dibromo-2,2-bis(bromomethyl)propane in water as solvent and non-toxic and cheap K ₄ [Fe(CN) ₆ ] as Nitrilation agent, by TBAB as phase-transfer catalyst and unliganded Cu (OAc) ₂ as catalyst catalytic synthesis 1,3-dicyano-2,2-two (nitrile methyl) propane, then 1,3- Dinitrile-2,2-bis(nitrile methyl)propane is hydrolyzed under the action of strong inorganic acid to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane. This method is simple, non-toxic and cheap, and the reaction The conditions are mild, the product yield is high and the purity is high, and polycarboxylic acids with longer carbon chains than raw material hydrocarbons can be obtained.

Thirdly, in the present invention, 1,3-dicarboxy-2,2-bis(acetoxy)propane and acetic anhydride undergo an exchange reaction under the action of catalyst glacial acetic acid to generate symmetrical product 2,4,8,10-tetracarbonyl- 3,9-dioxaspiro[5,5]undecane, the invention has simple operation, mild reaction conditions and pure product.

Description of drawings

Figure 1 is a molecular structure diagram of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane.

Figure 2 is a process route diagram for the preparation of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane.

Fig. 3 is an infrared spectrogram of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane.

Detailed ways

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with examples, but the present invention is not limited only to the following examples.

The anhydrous K ₄ Fe(CN) ₆ of the present invention is obtained through the following method. K ₄ Fe(CN) ₆ 3H ₂ O is ground into powder particles in a mortar, spread on a watch glass, and the watch glass Place in a vacuum drying oven at 75°C to dry. Of course, anhydrous K ₄ Fe(CN) ₆ obtained by other processes is also suitable for the present invention.

Example 1

The preparation method of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane, the steps are as follows:

(1) According to the molar ratio of 3:2, prepare nitrilation agent anhydrous K ₄ Fe(CN) ₆ and 1,3-dibromo-2,2-bis(bromomethyl)propane for subsequent use; according to transfer catalyst TBAB and The molar ratio of 1,3-dibromo-2,2-di(bromomethyl) _propane is 1:1 to prepare TBAB; Copper catalyst Cu(OAc) without ligand accounts for 10% of the total mass of phase transfer catalyst, According to the amount of solvent water and the mol ratio of copper catalyst being 5:1, water is taken for subsequent use;

Add Cu(OAc) ₂ catalyst to solvent water, stir until homogeneous, then add anhydrous K ₄ [Fe(CN) ₆ ], TBAB and 1,3-dibromo-2,2-bis(bromomethyl) Propane, seal the container and heat the reaction at 180°C for 50 minutes. After the reaction, let the system cool down to room temperature naturally, extract the product with ether three times, use a rotary evaporator to rotate the ether, GC detection and analysis, and make the product 1,3-di Nitrile-2,2-two (nitrile methyl) propane is purified by chromatographic column;

Reaction formula:

(2) Under a nitrogen atmosphere, add 2/3 of the total volume of required water to a reactor equipped with a stirrer at room temperature (the total amount of required water and 1,3-dinitrile-2,2- The molar ratio of bis(nitrile methyl)propane is 1:1.5); then pour 98% H ₂ SO ₄ , the molar ratio of sulfuric acid to 1,3-dicyano-2,2-bis(nitrile methyl)propane is 1: 1. Raise the temperature of the reaction system to 120°C, and then introduce the 1,3-dicyano-2,2-bis(nitrile methyl)propane prepared in the above steps within 1 hour, and control the temperature of the reaction system at 120°C , and then kept at this temperature for 20 minutes, added the remaining 1/3 of the total volume of water required within 10 minutes, and raised the temperature to 130°C for 6 hours, stopped stirring after the reaction, and separated the reaction medium to make it naturally After cooling to 90°C, the upper layer and the lower layer were separated to obtain 1,3-dicarboxy-2.2-di(acetoxy)propane. After distillation, extraction and recrystallization, the yield is 91%. The reaction formula is as follows:

(3) According to the molar ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane, acetic anhydride and catalyst glacial acetic acid as 1:2.1:0.15, 1,3-dicarboxy-2,2- Di(acetoxy)propane, acetic anhydride and glacial acetic acid were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction temperature was controlled at 90°C, and the reaction time was 12 hours until the reaction liquid was clarified and the reaction was completed; the reaction was completed After that, the heating was stopped, and the product was distilled under reduced pressure, and the residue was recrystallized from chloroform, filtered, dried and weighed to obtain 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[ 5,5] Undecane, yield 96.2%.

The reaction formula is as follows:

Fig. 3 is the infrared spectrum of the product obtained, and the analysis is as follows, so it is confirmed that the product obtained according to the method of the present invention is 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]dec One alkane.

Example 2

The preparation method of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane, the steps are as follows:

(1) According to the molar ratio of 4:3, prepare nitrilation agent anhydrous K ₄ Fe(CN) ₆ and 1,3-dibromo-2,2-bis(bromomethyl)propane for subsequent use; according to transfer catalyst TBAB and The molar ratio of 1,3-dibromo-2,2-bis(bromomethyl) _propane is 1:1.5 to prepare TBAB; Copper catalyst Cu(OAc) without ligand accounts for 9% of the total mass of phase transfer catalyst, According to the amount of solvent water and the mol ratio of copper catalyst being 7:1, water is taken for subsequent use;

Add Cu(OAc) ₂ catalyst to solvent water, stir until homogeneous, then add anhydrous K ₄ [Fe(CN) ₆ ], TBAB and 1,3-dibromo-2,2-bis(bromomethyl) Propane, seal the container and heat the reaction at 200°C for 75 minutes. After the reaction, let the system cool down to room temperature naturally, extract the product with ether three times, use a rotary evaporator to rotate the ether, GC detection and analysis, and make the product 1,3-di Nitrile-2,2-two (nitrile methyl) propane is purified by chromatographic column;

(2) Under a nitrogen atmosphere, add 2/3 of the total volume of required water to a reactor equipped with a stirrer at room temperature (the total amount of required water and 1,3-dinitrile-2,2- The molar ratio of bis(nitrile methyl)propane is 1:2.0); then pour 98% H ₂ SO ₄ , the molar ratio of sulfuric acid to 1,3-dicyano-2,2-bis(nitrile methyl)propane is 1.5: 1. Raise the temperature of the reaction system to 120°C, and then introduce the 1,3-dicyano-2,2-bis(nitrile methyl)propane prepared in the above steps within 1 hour, and control the temperature of the reaction system at 120°C , and then kept at this temperature for 40 minutes, added the remaining 1/3 of the total volume of water required within 10 minutes, and raised the temperature to 130°C for 6 hours, stopped stirring after the reaction, and separated the reaction medium to make it naturally Cool to 90°C, separate the upper and lower aqueous phases to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane, and the yield is 92.5% after distillation, extraction and recrystallization.

(3) According to the molar ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane, acetic anhydride and catalyst glacial acetic acid as 1:1.8:0.1, 1,3-dicarboxy-2,2- Di(acetoxy)propane, acetic anhydride and glacial acetic acid were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction temperature was controlled at 100°C, and the reaction time was 8 hours until the reaction liquid was clarified and the reaction was completed; the reaction was completed After that, the heating was stopped, and the product was distilled under reduced pressure, and the residue was recrystallized from chloroform, filtered, dried and weighed to obtain 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[ 5,5] Undecane, yield 97.6%.

Example 3

The preparation method of 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane, the steps are as follows:

(1) According to the molar ratio of 5:4, prepare nitrilation agent anhydrous K ₄ Fe(CN) ₆ and 1,3-dibromo-2,2-bis(bromomethyl)propane for subsequent use; according to transfer catalyst TBAB and The molar ratio of 1,3-dibromo-2,2-bis(bromomethyl)propane is 1:1.2 to prepare TBAB; Copper catalyst Cu(OAc) without ligand _accounts for 8% of the total mass of phase transfer catalyst, According to the amount of solvent water and the mol ratio of copper catalyst is 6:1 to take water for subsequent use;

Add Cu(OAc) ₂ catalyst to solvent water, stir until homogeneous, then add anhydrous K ₄ [Fe(CN) ₆ ], TBAB and 1,3-dibromo-2,2-bis(bromomethyl) Propane, seal the container and heat the reaction at 160°C for 80 minutes. After the reaction, let the system cool down to room temperature naturally, extract the product with ether three times, use a rotary evaporator to rotate the ether, GC detection and analysis, and make the product 1,3-di Nitrile-2,2-two (nitrile methyl) propane is purified by chromatographic column;

(2) Under a nitrogen atmosphere, add 2/3 of the total volume of required water to a reactor equipped with a stirrer at room temperature (the total amount of required water and 1,3-dinitrile-2,2- The molar ratio of bis(nitrile methyl)propane is 1:1.7); then pour 98% H ₂ SO ₄ , the molar ratio of sulfuric acid to 1,3-dicyano-2,2-bis(nitrile methyl)propane is 1.3: 1. Raise the temperature of the reaction system to 120°C, and then introduce the 1,3-dicyano-2,2-bis(nitrile methyl)propane prepared in the above steps within 1 hour, and control the temperature of the reaction system at 120°C , and then kept at this temperature for 30 minutes, added the remaining 1/3 of the total volume of water required within 10 minutes, and raised the temperature to 130°C for 6 hours, stopped stirring after the reaction, and separated the reaction medium to make it naturally After cooling to 90°C, the upper layer and the lower layer were separated to obtain 1,3-dicarboxy-2.2-di(acetoxy)propane. After distillation, extraction and recrystallization, the yield is 91.6%.

(3) According to the molar ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane, acetic anhydride and catalyst glacial acetic acid as 1:1.5:0.12, 1,3-dicarboxy-2,2- Di(acetoxy)propane, acetic anhydride and glacial acetic acid were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, the reaction temperature was controlled at 110°C, and the reaction time was 6 hours until the reaction liquid was clarified and the reaction was completed; the reaction was completed After that, the heating was stopped, and the product was distilled under reduced pressure, and the residue was recrystallized from chloroform, filtered, dried and weighed to obtain 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[ 5,5] Undecane, yield 98.5%.

Application example:

The novel spiro compound-spiro tetracarboxylic dianhydride (2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5.5]undecane) is a new type of epoxy resin The expansion curing agent of the system is mainly used in the field of epoxy resin casting and fiber reinforced composite materials to reduce the volume shrinkage of epoxy resin and its composite materials during the curing process. The volume shrinkage of the epoxy resin system is reduced to 0~0.5%.

The application method is as follows: in parts by weight, 100 parts of E51 epoxy resin; 33 parts of spirocyclotetracarboxylic dianhydride, mix evenly, pour, defoam, heat to 150°C for 4 hours; 170°C for 2 hours; 190°C for 2 hours Curing for 2 hours; curing at 210°C for 2 hours, using a dilatometer to track and measure the volume change of the reaction system, and determine that the volume shrinkage of the epoxy resin during the curing process is less than 0.5%.

Claims (8)

1. The synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane is characterized in that it is divided into three steps: (1) By polyhalogenated hydrocarbon 1,3-dibromo-2,2-di(bromomethyl)propane with water as solvent, under the action of nitrilation agent, by phase transfer catalyst and ligand-free copper catalyst Catalytic synthesis of 1,3-dicyano-2,2-bis(nitrile methyl)propane; (2) 1,3-dicarboxy-2,2-bis(nitrile methyl)propane is hydrolyzed under the action of strong inorganic acid to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane; (3) The exchange reaction of 1,3-dicarboxy-2,2-di(acetoxy)propane and acetic anhydride under the action of a catalyst produces the symmetrical product 2,4,8,10-tetracarbonyl-3,9-di Oxaspiro[5,5]undecane; Wherein, the phase transfer catalyst is tetrabutylammonium bromide, the copper catalyst without ligand is Cu(OAc) ₂ ; the nitrilation agent is anhydrous K ₄ Fe(CN) ₆ ; the inorganic strong acid is 98 % concentrated sulfuric acid; the catalyzer of described step (3) is glacial acetic acid. 2. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that said solvent The molar ratio of water to ligand-free copper catalyst is 5:1-7:1. 3. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that said nitrile The oxidizing agent is anhydrous K ₄ Fe(CN) ₆ , and the molar ratio of anhydrous K ₄ Fe(CN) ₆ to polyhalogenated hydrocarbon 1,3-dibromo-2,2-bis(bromomethyl)propane is 3 :2～5:4. 4. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that the phase The molar ratio of transfer catalyst tetrabutylammonium bromide to polyhalogenated hydrocarbon 1,3-dibromo-2,2-di(bromomethyl)propane is 1:1～1:1.5, and the ligand-free copper catalyst Cu (OAc) ₂ accounts for 8%-10% of the total mass of the phase transfer catalyst. 5. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that said step (1) The reaction temperature is 160°C-200°C, and the reaction time is 50-80min. 6. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that the hydrolysis The reaction step is to react 1,3-dicyano-2,2-bis(nitrile methyl)propane with water in the presence of a strong inorganic acid, and the amount of the hydrolysis reaction water is equal to that of 1,3-dicyano-2, The molar ratio of 2-bis(nitrile methyl)propane is 1:1.5～1:2.0; the strong inorganic acid is 98% concentrated sulfuric acid, concentrated sulfuric acid and 1,3-dicyano-2,2-bis(nitrile base) The molar ratio of propane is 1:1～1.5:1. 7. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that said step The catalyst in (3) is glacial acetic acid, and the catalyst is 0.1 to 0.15 times the molar weight of the reactant 1,3-dicarboxy-2,2-bis(acetoxy)propane; in the step (3), 1, The molar ratio of 3-dicarboxy-2,2-bis(acetoxy)propane to acetic anhydride is 1:1.5-2.1; the reaction temperature in the step (3) is 90-110°C, and the reaction time is 6-12h . 8. the synthetic method of spiro compound 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane according to claim 1, is characterized in that concrete steps are as follows : (1) According to the molar ratio of 3:2 to 5:4, prepare the anhydrous K ₄ Fe(CN) ₆ and 1,3-dibromo-2,2-bis(bromomethyl)propane as the nitrilation agent for later use; The molar ratio of transfer catalyst tetrabutylammonium bromide to 1,3-dibromo-2,2-di(bromomethyl)propane is 1:1～1:1.5 to prepare TBAB; ligand-free copper catalyst Cu(OAc ) ₂ accounts for 8% to 10% of the total mass of the phase transfer catalyst; according to the molar ratio of the amount of solvent water to the copper catalyst being 5:1 to 7:1, water is taken for later use; Add Cu(OAc) ₂ catalyst to solvent water, stir until homogeneous, then add anhydrous K ₄ [Fe(CN) ₆ ], tetrabutylammonium bromide and 1,3-dibromo-2,2-di (Bromomethyl)propane, seal the container and heat the reaction at 160°C to 200°C for 50min to 80min. After the reaction, let the system cool down to room temperature naturally, extract the product with ether three times, and use a rotary evaporator to spin distill the ether and detect it by GC. Analysis, and make product 1,3-dicyano-2,2-bis(nitrile methyl) propane pass through chromatographic column purification; (2) Under a nitrogen atmosphere, add 2/3 of the total volume of water required to the reactor equipped with a stirrer at room temperature, the total volume of water required and 1,3-dinitrile-2,2- The molar ratio of bis(nitrile methyl)propane is 1:1.5～1:2.0; then pour 98% H ₂ SO ₄ , sulfuric acid and 1,3-dicyano-2,2-bis(nitrile methyl)propane Ratio 1:1～1.5:1, raise the temperature of the reaction system to 120°C, and then introduce the 1,3-dicyano-2,2-bis(nitrile methyl)propane prepared in the above steps within 1h, and react The temperature of the system is controlled at 120°C, and then kept at this temperature for 20 to 40 minutes, then add the remaining 1/3 of the total volume of water required within 10 minutes, and raise the temperature to 130°C for 6 hours, and stop stirring after the reaction is completed. The reaction medium was separated into layers, allowed to cool naturally to 90°C, and the upper layer and the lower layer were separated to obtain 1,3-dicarboxy-2.2-bis(acetoxy)propane; (3) According to the molar feed ratio of 1,3-dicarboxy-2,2-di(acetoxy)propane and acetic anhydride is 1:1.5～2.1, the catalyst glacial acetic acid is 1,3-dicarboxy-2,2- 0.1 to 0.15 times the molar amount of bis(acetoxy)propane, put 1,3-dicarboxy-2,2-bis(acetoxy)propane, acetic anhydride and glacial acetic acid in a place with agitator, reflux condenser and In the three-necked flask with a thermometer, the reaction temperature is controlled at 90-110°C, and the reaction time is 6-12 hours until the reaction liquid is clarified and the reaction is completed; stop heating after the reaction is completed, and the product is distilled under reduced pressure, and the residue is reconstituted with chloroform. Crystallize, filter, dry and weigh to obtain 2,4,8,10-tetracarbonyl-3,9-dioxaspiro[5,5]undecane.