A low-curing-shrinkage epoxy resin, its preparation method and application

Abstract

This invention belongs to the field of epoxy resin technology, specifically relating to a low-curing-shrinkage epoxy resin, its preparation method, and its application. This invention provides a low-curing-shrinkage epoxy resin having the structure shown in Formula 1; wherein R has the structure shown in Formula 2; and n is any integer from 1 to 2. This invention introduces tetraoxaspirocyclic groups into the epoxy resin molecular chain. Under the action of BF3 amine curing agent, the tetraoxaspirocyclic groups can undergo a ring-opening reaction, changing the molecular chain from a cyclic structure to a linear state. This increases the volume of the low-curing-shrinkage epoxy resin molecular chain, effectively filling the space shrinkage caused by the curing reaction during resin curing, fundamentally solving the problem of epoxy resin curing shrinkage, and thus avoiding residual stress from curing shrinkage during epoxy resin curing.

Description

Technical Field

[0001] This invention belongs to the field of epoxy resin technology, specifically relating to a low-curing-shrinkage epoxy resin, its preparation method, and its application. Background Technology

[0002] Epoxy resins possess many excellent properties, such as superior mechanical properties, adhesive properties, corrosion resistance, and electrical insulation, and are widely used in the packaging of electronic components, integrated circuits, and transformers. However, in fields with high requirements for curing shrinkage, such as electronic packaging, epoxy composite materials, and epoxy adhesives in aerospace, the residual stress generated by curing shrinkage can lead to safety hazards such as cracks and mechanical weaknesses, limiting further applications.

[0003] The residual stress generated during epoxy resin curing mainly includes temperature internal stress and curing internal stress. Temperature internal stress is caused by the resin's thermal expansion or contraction during curing due to temperature changes, and can be reduced by controlling the temperature through staged curing. Curing internal stress, on the other hand, is caused by the chemical shrinkage of the resin during the curing cross-linking reaction, and is determined by the properties of the resin system itself, making it difficult to change. Currently, the main solutions to the epoxy resin curing shrinkage problem focus on the following: 1) Introducing resins with fewer functional groups to reduce the curing shrinkage rate; 2) Adding a certain amount of toughening agent to distribute the internal stress evenly; 3) Adding an appropriate amount of inorganic filler to reduce the shrinkage rate and coefficient of thermal expansion; 4) Lowering the curing temperature as much as possible while extending the reaction time; 5) Using a staged curing method, initially using low-temperature curing and gradually using medium-high temperature curing in the later stages; 6) Ensuring that the heating and cooling processes are not too rapid, so that the resin expansion and contraction occur more slowly and evenly. However, the above solutions only reduce stress or prevent localized stress concentration, and do not fundamentally solve the stress problem caused by curing shrinkage. Summary of the Invention

[0004] In view of this, the present invention provides a low-curing-shrinkage epoxy resin, its preparation method and application. The low-curing-shrinkage epoxy resin provided by the present invention does not shrink during the curing process, thereby avoiding residual stress during the curing process.

[0005] To solve the above-mentioned technical problems, the present invention provides a low-curing-shrinkage epoxy resin having the structure shown in Formula 1:

[0006]

[0007] Wherein, R has the structure shown in Equation 2:

[0008]

[0009] n is any integer from 1 to 2.

[0010] Preferably, the epoxy equivalent of the low-curing-shrinkage epoxy resin is 350-450 g / mol.

[0011] The present invention also provides a method for preparing the low-curing-shrinkage epoxy resin described in the above technical solution, comprising the following steps:

[0012] Trimethylolpropane, di-n-butyltin oxide, and a first organic solvent were mixed and subjected to a coordination cyclization reaction to obtain an intermediate; the intermediate has the structure shown in Formula 3:

[0013]

[0014] The intermediate, carbon disulfide, and the second organic solvent were mixed and subjected to a coordination elimination reaction to obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane;

[0015] The 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane, 1,6-hexamethylene diisocyanate, and a third organic solvent are mixed and subjected to an esterification reaction. Then, the mixture is further subjected to an amino esterification reaction with epoxy resin to obtain the low-curing-shrinkage epoxy resin.

[0016] Preferably, the mass ratio of trimethylolpropane to di-n-butyltin oxide is 100:180-225.

[0017] The coordination cyclization reaction is carried out at a temperature of 100–120°C for 6–10 hours.

[0018] Preferably, the mass ratio of the intermediate to carbon disulfide is 100:10 to 12;

[0019] The temperature of the coordination elimination reaction is 80–110°C, and the time of the coordination elimination reaction is 8–12 h.

[0020] Preferably, the mass ratio of 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane to 1,6-hexamethylene diisocyanate is 100:60-80;

[0021] The esterification reaction is carried out at a temperature of 40–60°C for 1–2 hours.

[0022] Preferably, the epoxy resin is a bisphenol A type epoxy resin, and the epoxy equivalent of the bisphenol A type epoxy resin is 250-450 g / mol;

[0023] The mass ratio of the esterification reaction product to the epoxy resin is 100:250 to 450.

[0024] Preferably, the temperature of the amino esterification reaction is 40–60°C, and the time of the amino esterification reaction is 2–4 hours.

[0025] The present invention also provides the application of the low-curing shrinkage epoxy resin described in the above technical solution or the low-curing shrinkage epoxy resin prepared by the preparation method described in the above technical solution in epoxy adhesives in electronic packaging, epoxy composite materials, and aerospace fields;

[0026] The curing agent used in this application is BF3 amine curing agent.

[0027] Preferably, the application method includes the following steps: mixing the low-curing-shrinkage epoxy resin with BF3 curing agent and then curing it.

[0028] This invention provides a low-curing-shrinkage epoxy resin having the structure shown in Formula 1:

[0029]

[0030] Wherein, R has the structure shown in Equation 2:

[0031] n is any integer from 1 to 2. This invention introduces tetraoxaspirocyclic groups into the epoxy resin molecular chain. Under the action of BF3 amine curing agent, the tetraoxaspirocyclic groups can undergo a ring-opening reaction, changing the molecular chain from a cyclic structure to a linear state. This increases the volume of the low-curing-shrinkage epoxy resin molecular chain, effectively filling the space shrinkage caused by the curing reaction during resin curing. This fundamentally solves the problem of epoxy resin curing shrinkage, thus avoiding residual stress from curing shrinkage during the curing process. Detailed Implementation

[0032] This invention provides a low-curing-shrinkage epoxy resin having the structure shown in Formula 1:

[0033]

[0034] Wherein, R has the structure shown in Equation 2:

[0035]

[0036] n is any integer from 1 to 2.

[0037] In this invention, the epoxy equivalent of the low-curing-shrinkage epoxy resin is preferably 350-450 g / mol, more preferably 385-412 g / mol.

[0038] In this invention, R... It serves as a grafting agent, used to graft tetraoxane spirocyclic groups onto the epoxy resin molecular chain; R in It plays a role in resisting curing shrinkage. Under the action of BF3 amine curing agent, the tetraoxaspirocyclic group can undergo a ring-opening reaction, and its molecular chain changes from a cyclic structure to a straight chain state, thereby increasing the volume of the molecular chain and avoiding space shrinkage of epoxy resin during curing, thus avoiding residual stress of curing shrinkage of epoxy resin during curing.

[0039] The present invention also provides a method for preparing the low-curing-shrinkage epoxy resin described in the above technical solution, comprising the following steps:

[0040] Trimethylolpropane, di-n-butyltin oxide, and a first organic solvent were mixed and subjected to a coordination cyclization reaction to obtain an intermediate; the intermediate has the structure shown in Formula 3:

[0041]

[0042] The intermediate, carbon disulfide, and the second organic solvent were mixed and subjected to a coordination elimination reaction to obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane;

[0043] The 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane, 1,6-hexamethylene diisocyanate, and a third organic solvent are mixed and subjected to an esterification reaction. Then, the mixture is further subjected to an amino esterification reaction with epoxy resin to obtain the low-curing-shrinkage epoxy resin.

[0044] This invention involves a coordination cyclization reaction of trimethylolpropane, di-n-butyltin oxide, and a first organic solvent to obtain an intermediate. The intermediate has the structure shown in Formula 3, where n-Bu is a n-butyl group. In this invention, the first mixture preferably includes the following steps:

[0045] Trimethylolpropane was dissolved in a first organic solvent to obtain a trimethylolpropane solution;

[0046] The trimethylolpropane solution and di-n-butyltin oxide were mixed to obtain the solution to be reacted.

[0047] This invention involves dissolving trimethylolpropane in a first organic solvent to obtain a trimethylolpropane solution. In this invention, the first organic solvent is preferably toluene, benzene, or xylene, more preferably toluene. In this invention, the mass ratio of trimethylolpropane to the first organic solvent is preferably 134:145-155, more preferably 134:150.

[0048] In this invention, the dissolution is preferably carried out under stirring conditions, and the stirring speed is preferably 200-500 r / min, more preferably 300-400 r / min. This invention does not have special requirements for the stirring time, as long as complete dissolution is achieved.

[0049] After obtaining a trimethylolpropane solution, the present invention further mixes the trimethylolpropane solution with di-n-butyltin oxide to obtain a reaction solution. In the present invention, the mass ratio of trimethylolpropane to di-n-butyltin oxide is preferably 100:180-225, more preferably 100:190-210. In the present invention, the fifth mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 200-500 r / min, more preferably 300-400 r / min. The present invention has no special requirements on the time of the fifth mixing, as long as the mixture is homogeneous.

[0050] In this invention, the temperature of the coordination cyclization reaction is preferably 100-120°C, more preferably 110-115°C; the time of the coordination cyclization reaction is preferably 6-10 h, more preferably 8-10 h.

[0051] In this invention, the coordination cyclization reaction is preferably accompanied by stirring, and the stirring speed is preferably 200-500 r / min, more preferably 300-400 r / min.

[0052] In this invention, the coordination cyclization reaction preferably further includes: post-treatment of the system after the coordination cyclization reaction to remove the first organic solvent and residual di-n-butyltin oxide. This invention preferably uses vacuum distillation to remove the first organic solvent, the temperature of which is preferably 120–140°C, more preferably 130°C; the vacuum degree of which is preferably 0.008–0.012 MPa, more preferably 0.01 MPa. This invention preferably uses n-hexane as a washing solution to wash the system after removing the first organic solvent to remove residual di-n-butyltin oxide.

[0053] After obtaining the intermediate, the present invention performs a coordination elimination reaction on the intermediate, carbon disulfide, and a second organic solvent to obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane. In the present invention, the second mixture preferably includes the following steps:

[0054] The intermediate is dissolved in a second organic solvent to obtain an intermediate solution;

[0055] Carbon disulfide was added dropwise to the intermediate solution.

[0056] This invention involves dissolving an intermediate in a second organic solvent to obtain an intermediate solution. In this invention, the second organic solvent is preferably toluene, benzene, or xylene, more preferably toluene. In this invention, the mass ratio of the intermediate to the second organic solvent is preferably 100:145-155, more preferably 100:150.

[0057] In this invention, the dissolution is preferably carried out under stirring conditions, and the stirring speed is preferably 200-400 r / min, more preferably 300-400 r / min. This invention does not have special requirements for the stirring time, as long as complete dissolution is achieved.

[0058] After obtaining the intermediate solution, carbon disulfide is added dropwise to the intermediate solution in this invention. In this invention, the mass ratio of the intermediate to carbon disulfide is preferably 100:10-12, more preferably 100:11-12. In this invention, the dropping rate is preferably 3-6 g / h, more preferably 4-6 parts / h. In this invention, the dropping is preferably accompanied by stirring. In this invention, the stirring speed is preferably 200-400 r / min, more preferably 300-400 r / min.

[0059] In this invention, the temperature of the coordination elimination reaction is preferably 80-110°C, more preferably 85-100°C; the time of the coordination elimination reaction is preferably 8-12 hours, more preferably 10-12 hours.

[0060] In this invention, the coordination elimination reaction is preferably accompanied by stirring, and the stirring speed is preferably 200-400 r / min, more preferably 300-400 r / min.

[0061] In this invention, the process preferably further includes removing the solvent from the system after the coordination elimination reaction. This invention does not have specific requirements regarding the method of removing the solvent from the system after the coordination elimination reaction; conventional methods in the art are sufficient.

[0062] After obtaining 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane, the present invention further mixes the 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane, 1,6-hexamethylene diisocyanate, and a third organic solvent, performs an esterification reaction, and then mixes it with an epoxy resin for a fourth amino esterification reaction to obtain the low-curing-shrinkage epoxy resin. In the present invention, the third mixing preferably includes the following steps:

[0063] The 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane was dissolved in a third organic solvent to obtain a 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane solution;

[0064] The solution of 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane was mixed with 1,6-hexamethylene diisocyanate.

[0065] In this invention, 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane is dissolved in a third organic solvent to obtain a 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane solution. In this invention, the third organic solvent is preferably toluene, benzene, or xylene, more preferably toluene. In this invention, the mass ratio of 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane to the third organic solvent is preferably 26.4:90 to 110, more preferably 26.4:100.

[0066] The present invention has no special requirements for the dissolution, as long as it can be completely dissolved.

[0067] After obtaining a solution of 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane, the present invention further mixes the 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane solution with 1,6-hexamethylene diisocyanate. In the present invention, the mass ratio of the 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclic[5,5]undecane to 1,6-hexamethylene diisocyanate is 100:60 to 80, more preferably 100:63 to 70. The present invention has no special requirements for the sixth mixing step, as long as the mixture is homogeneous.

[0068] In this invention, the temperature of the esterification reaction is preferably 40-60°C, more preferably 50-55°C; the time of the esterification reaction is preferably 1-2 hours, more preferably 1-1.5 hours.

[0069] In this invention, the epoxy resin is preferably a bisphenol A type epoxy resin, and the epoxy equivalent of the bisphenol A type epoxy resin is preferably 250-450 g / mol, more preferably 300-350 g / mol. In this invention, the mass ratio of the esterification reaction product to the epoxy resin is 100:250-450, more preferably 100:280-410.

[0070] The present invention has no special requirements for the fourth mixing step, as long as the mixture can be mixed evenly.

[0071] In this invention, the temperature of the amino esterification reaction is preferably 40-60°C, more preferably 50-55°C; the time of the amino esterification reaction is preferably 2-4 hours, more preferably 2.5-3 hours.

[0072] The present invention preferably involves solvent removal from the system following the amino esterification reaction. The present invention does not specify a particular method for solvent removal; any method conventional in the art may be used.

[0073] This invention also provides the application of the low-curing-shrinkage epoxy resin described in the above-described technical solutions or the low-curing-shrinkage epoxy resin prepared by the preparation method described in the above-described technical solutions in epoxy adhesives for electronic packaging, epoxy composites, and aerospace applications. In this invention, epoxy adhesives for electronic packaging, epoxy composites, and aerospace applications have high requirements for curing shrinkage rate. In this invention, the application method preferably includes the following steps: mixing the low-curing-shrinkage epoxy resin with a BF3 amine curing agent and then curing. This invention does not have special requirements for the mixing, as long as it can be mixed evenly. In this invention, degassing is preferably performed before curing, and the degassing temperature is preferably 78–52°C, more preferably 80°C. In this invention, the curing temperature is preferably 110–130°C, more preferably 120°C, and the curing time is preferably 3–5 hours, more preferably 4 hours.

[0074] In this invention, the curing agent used in the application is BF3 amine curing agent.

[0075] In this invention, the equation for the ring-opening reaction of the tetraoxaspirocyclic group in the low-curing-shrinkage epoxy resin under the action of BF3 amine curing agent is shown in equation a:

[0076]

[0077] This invention addresses the shrinkage problem of epoxy resin during curing by introducing a tetraoxaspirocyclic compound into the epoxy resin molecular chain. Utilizing the ring-opening reaction during curing, which involves volume expansion as the cyclic molecule transforms into a chain molecule, this fundamentally prevents stress concentration during curing. Simultaneously, the ring-opening process increases the crosslinking density of the epoxy resin, improving its heat resistance and impact toughness.

[0078] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0079] In the embodiments, the amount of raw materials used is measured in parts by mass. This invention does not have special requirements on the weight of raw materials used, as long as the proportion of parts by mass is met.

[0080] Example 1

[0081] 134 parts of trimethylolpropane were dissolved in 150 parts of toluene under stirring at 300 r / min to obtain a trimethylolpropane solution; the trimethylolpropane solution and 275 parts of di-n-butyltin oxide were mixed at 300 r / min and subjected to a coordination cyclization reaction at 110 °C for 10 h to obtain an intermediate; toluene was removed from the system after the coordination cyclization reaction by depressurization, and residual di-n-butyltin oxide was washed away with n-hexane;

[0082] 100 parts of the intermediate were dissolved in 150 parts of toluene. 11 parts of carbon disulfide were added dropwise at a rate of 5 g / h under a rotation speed of 400 r / min. The reaction was carried out at 85 °C for 12 h to remove toluene and obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane.

[0083] 26.4 parts of 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspirocyclo[5,5]undecane were dissolved in 100 parts of toluene and then mixed with 16.6 parts of 1,6-hexamethylene diisocyanate under stirring. After esterification at 55°C (with stirring) for 1 h, 120 parts of bisphenol A epoxy resin (epoxy equivalent of 315 g / mol) were added and subjected to amino esterification at 55°C (with stirring) for 3 h. Toluene was then removed to obtain a low-curing-shrinkage epoxy resin.

[0084] Example 2

[0085] The low-curing-shrinkage epoxy resin was prepared according to the method of Example 1, except that the amount of bisphenol A epoxy resin (epoxy equivalent of 315 g / mol) added was 150 parts.

[0086] Example 3

[0087] The low-curing-shrinkage epoxy resin was prepared according to the method of Example 1, except that the amount of bisphenol A epoxy resin (epoxy equivalent of 315 g / mol) added was 180 parts.

[0088] Comparative Example 1

[0089] E-51 epoxy resin was used as a comparative example.

[0090] The epoxy equivalent of the low-curing shrinkage epoxy resins prepared in Examples 1 to 3 was determined according to GB / T 4612-2008 Determination of Epoxy Equivalent in Plastic Epoxy Compounds. The results are listed in Table 1.

[0091] Table 1. Epoxy equivalent of the low-curing shrinkage epoxy resins prepared in Examples 1-3

[0092] Example Epoxy equivalent (g / mol) Example 1 412 Example 2 398 Example 3 384

[0093] As can be seen from Table 1, the epoxy equivalent is inconsistent due to the different amounts of epoxy resin used in the examples. The higher the resin content, the lower the equivalent.

[0094] The low-curing-shrinkage epoxy resins prepared in Examples 1-3 and ordinary bisphenol A epoxy resins (epoxy equivalent of 315 g / mol) were cured under the action of BF3 o-phenylenediamine complex. During the curing process, the volume was monitored using a dilatometer, and the glass transition temperature of the cured product was tested using DSC to compare its heat resistance. The impact toughness was tested according to the method for testing the impact strength of the cured product in GB / T 2567-2021. The test results are listed in Table 2.

[0095] Table 2 Performance parameters of epoxy resins in Examples 1-3 and Comparative Example 1

[0096] performance Example 1 Example 2 Example 3 Comparative Example 1 Curing shrinkage rate (%) 0.2 0.3 0.4 2.2 Glass transition temperature (°C) 167.8 162.5 161.2 126.3 <![CDATA[Impact strength (kJ / m 2 )]]> 23.2 22.4 20.5 14.6

[0097] According to the test results in Table 2, the low-curing-shrinkage epoxy resin provided by this invention has significantly better curing shrinkage rate, glass transition temperature, and impact strength than ordinary epoxy resin.

[0098] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A low cure shrinkage epoxy resin characterized by, The preparation method of the low-curing shrinkage epoxy resin comprises the following steps: The trimethylolpropane, di-n-butyl tin oxide and a first organic solvent are first mixed to perform a coordination cyclization reaction to obtain an intermediate; the intermediate has a structure shown in formula 3: Formula 3; The intermediate, carbon disulfide and a second organic solvent are second mixed to perform a coordination elimination reaction to obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane; The 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane, 1,6-hexamethylene diisocyanate and a third organic solvent are third mixed to perform an esterification reaction, and then an epoxy resin is fourth mixed to perform an amine group esterification reaction to obtain the low-curing shrinkage epoxy resin; the epoxy resin is a bisphenol A type epoxy resin; the mass ratio of the 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane and the 1,6-hexamethylene diisocyanate is 100:60-80; the temperature of the esterification reaction is 40-60 DEG C, and the time of the esterification reaction is 1-2 h; the temperature of the amine group esterification reaction is 40-60 DEG C, and the time of the amine group esterification reaction is 2-4 h.

2. The low cure shrinkage epoxy resin of claim 1, wherein, The epoxy equivalent weight of the low-curing shrinkage epoxy resin is 350-450 g / mol.

3. The preparation method of the low-curing shrinkage epoxy resin in claim 1 or 2, comprising the following steps: The trimethylolpropane, di-n-butyl tin oxide and a first organic solvent are first mixed to perform a coordination cyclization reaction to obtain an intermediate; the intermediate has a structure shown in formula 3: Formula 3; The intermediate, carbon disulfide and a second organic solvent are second mixed to perform a coordination elimination reaction to obtain 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane; The 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane, 1,6-hexamethylene diisocyanate and a third organic solvent are third mixed to perform an esterification reaction, and then an epoxy resin is fourth mixed to perform an amine group esterification reaction to obtain the low-curing shrinkage epoxy resin; the epoxy resin is a bisphenol A type epoxy resin; the mass ratio of the 3,9-dihydroxymethyl-3',9'-diethyl-1,5,7,11-tetraoxaspiro[5,5]undecane and the 1,6-hexamethylene diisocyanate is 100:60-80; the temperature of the esterification reaction is 40-60 DEG C, and the time of the esterification reaction is 1-2 h; the temperature of the amine group esterification reaction is 40-60 DEG C, and the time of the amine group esterification reaction is 2-4 h.

4. The production method according to claim 3, characterized by, The mass ratio of the trimethylolpropane and the di-n-butyl tin oxide is 100:180-225; The temperature of the coordination cyclization reaction is 100-120 DEG C, and the time of the coordination cyclization reaction is 6-10 h.

5. The preparation method according to claim 3, characterized in that, The mass ratio of the intermediate and the carbon disulfide is 100:10-12; The temperature of the coordination elimination reaction is 80-110℃, and the time of the coordination elimination reaction is 8-12h.

6. The preparation method according to claim 3, characterized in that, The bisphenol A type epoxy resin has an epoxy equivalent weight of 250-450g / mol. The mass ratio of the product of the esterification reaction to the epoxy resin is 100:250-450.

7. The use of the low-curing shrinkage epoxy resin of claim 1 or 2 or the low-curing shrinkage epoxy resin prepared by the preparation method of any one of claims 3-6 in electronic packaging, epoxy composite materials, and epoxy adhesives in the field of aerospace. The curing agent used in the use is a BF3 amine curing agent.

8. Use according to claim 7, characterized in that, The application method comprises the following steps: mixing the low-curing shrinkage epoxy resin with the BF3 amine curing agent and then curing.

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