阅读说明：本技术 复合固化剂以及由该复合固化剂制备的环氧树脂组合物 (Composite curing agent and epoxy resin composition prepared from same ) 是由 郭永军 余家斌 梁荣强 漆小龙 于 2020-12-28 设计创作，主要内容包括：本发明涉及一种复合固化剂以及由该复合固化剂制备的环氧树脂组合物,所述的复合固化剂包括改性胺类固化剂、有机酰肼以及路易斯酸胺络合物。以此为固化剂制备所得的环氧树脂组合物,其固化温度为120℃,所需完全固化时长控制在8min～12min,其固化温度为150℃,所需完全固化时长控制在5min～10min,固化反应所需温度和所需时长合适,既没有降低固化效率,还能保持固化反应温和,从而有效避免反应剧烈导致反应放热大、易爆聚、固化成型后脆性很大、弯曲强度低以及尺寸稳定性差等。并且以该固化剂为制备原料,能够与环氧树脂、促进剂和溶剂混合即可制备获得环氧树脂组合物,工艺简单,生产效益高。(The invention relates to a composite curing agent and an epoxy resin composition prepared from the same. The epoxy resin composition prepared by using the epoxy resin as the curing agent has the curing temperature of 120 ℃, the required complete curing time is controlled to be 8-12 min, the curing temperature is 150 ℃, the required complete curing time is controlled to be 5-10 min, the temperature and the required time for the curing reaction are proper, the curing efficiency is not reduced, and the curing reaction is kept mild, so that the problems of large reaction heat release, easy implosion, large brittleness after curing and forming, low bending strength, poor size stability and the like caused by violent reaction are effectively avoided. The curing agent is used as a preparation raw material, can be mixed with epoxy resin, an accelerant and a solvent to prepare the epoxy resin composition, and has the advantages of simple process and high production benefit.)

1. The composite curing agent is characterized by comprising a modified amine curing agent, an organic hydrazide and a Lewis acid-amine complex.

2. The composite curing agent of claim 1, wherein the mass ratio of the modified amine curing agent to the organic hydrazide to the lewis acid-amine complex compound is (2.5-3.5) to (0.5-1.5): (0.5 to 1.5).

3. The composite curing agent according to claim 1 or 2, wherein the modified amine curing agent is an aliphatic amine curing agent.

4. The composite curing agent according to claim 3, wherein the aliphatic amine curing agent is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

5. The composite curing agent according to any one of claims 1, 2 and 4, wherein the organic hydrazide is at least one selected from the group consisting of sebacic dihydrazide, adipic dihydrazide, terephthalic dihydrazide and isophthalic hydrazide.

6. The composite curing agent according to any one of claims 1, 2 and 4, wherein the Lewis acid amine complex is at least one selected from the group consisting of boron trifluoride amine complex and boron trichloride amine complex.

7. The composite curing agent according to claim 6, wherein the boron trifluoride amine complex is at least one selected from the group consisting of boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, and boron trifluoride-triethanolamine complex; or/and the boron trichloride amine complex is boron trichloride-octylamine complex.

8. An epoxy resin composition, characterized in that the raw materials for preparing the epoxy resin composition comprise epoxy resin, a curing agent, an accelerator and a solvent, wherein the curing agent is the composite curing agent of any one of claims 1 to 7.

9. The epoxy resin composition according to claim 8, wherein the epoxy resin composition is prepared from the following raw materials in parts by mass:

10. the epoxy resin composition according to claim 8 or 9, wherein the epoxy resin is at least one selected from the group consisting of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an aliphatic glycidyl ether epoxy resin, and a glycidyl ester type epoxy resin.

11. The epoxy resin composition according to claim 8 or 9, wherein the accelerator is selected from the group consisting of urea amine accelerators.

12. The epoxy resin composition of claim 11, wherein the urea amine accelerator is at least one member selected from the group consisting of N-p-chlorophenyl-N, N-dimethyl urea (chlorourea), N- (3, 4-dichlorophenyl) -N, N-dimethyl urea, N- (3-phenyl) -N, N-dimethyl urea, N- (4-phenyl) -N, N-dimethyl urea, 2-methylimidazolium urea, and thiourea.

13. The epoxy resin composition as claimed in claim 8, 9 or 12, wherein the solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone and propylene glycol methyl ether.

14. The epoxy resin composition according to claim 8, 9 or 12, wherein the raw material for preparing the epoxy resin composition further comprises an ambient temperature stabilizer.

15. The epoxy resin composition according to claim 14, wherein the ambient temperature stabilizer is at least one selected from the group consisting of alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and phenyl glycidyl ether.

16. The method for preparing the epoxy resin composition according to any one of claims 8 to 15, wherein the method comprises the steps of: mixing the above raw materials.

Technical Field

The invention relates to the technical field of epoxy resin materials, in particular to a composite curing agent and an epoxy resin composition prepared from the composite curing agent.

Background

With the development of science and technology, the demand on an epoxy resin system becomes wider, and the epoxy resin-based composite material has the advantages of high specific modulus, high specific strength, fatigue resistance, corrosion resistance, high integral forming and designability and the like, and has wide application prospects in the fields of aerospace, automobile manufacturing, sports goods, molded products and the like. However, the conventional epoxy resin composition has low reactivity and long curing time, and not only reduces the production efficiency, but also increases the production cost. The fast curing epoxy resin composition realizes fast curing of resin at a specific temperature, improves the production efficiency and reduces the production cost.

At present, epoxy resin compositions capable of being rapidly cured on the market are generally divided into non-latent low-temperature rapid curing and latent high-temperature rapid curing, and the latent medium-temperature curing epoxy resins are few and have the problems of short storage life, low storage temperature and the like. Conventional fast curing epoxy resin compositions, such as a fast curing epoxy resin system, consist of a cured resin having a TG of no more than 140 ℃, one or more urea-based curing agents, dicyandiamide. The curing of the traditional fast curing epoxy resin product is specifically as follows: 150 ℃ is not more than 150 seconds, 120 ℃ is not more than 4 minutes, the curing temperature and the curing time of the epoxy resin composition are not harmonious, the reaction is too violent, and the storage stability is poor. For another example, the fast curing epoxy resin matrix for the prepreg comprises the following chemical components in parts by mass: 60-100 parts of epoxy resin, 20-40 parts of curing agent, 0.5-3 parts of accelerator and 5-30 parts of toughening agent, wherein the curing agent is a mixture of dicyandiamide and modified amine, and the mass part ratio of the modified amine to the dicyandiamide is (1-20): 1. The curing temperature is 130-150 ℃, and the curing time is less than or equal to 20 minutes. In practice, however, the curing temperature and curing time of the epoxy resin matrix are inconsistent, and the preparation method of the epoxy resin matrix comprises the steps of mixing the epoxy resin and the toughening agent, heating to 150-180 ℃, uniformly stirring, cooling to 70-100 ℃, adding the modified amine in the curing agent, stirring until the modified amine is dissolved, adding the dicyandiamide in the curing agent, continuously stirring to be uniform, then continuously cooling to 60-70 ℃, adding the accelerator, and continuously stirring to be uniform to obtain the rapidly-cured epoxy resin matrix, wherein the preparation process is particularly complex.

In general, conventional fast-curing epoxy resin compositions have a problem that the temperature required for curing and the time required for curing are not compatible. The temperature required for curing is relatively high, the time required for curing is relatively short, the curing reaction is relatively violent, the heat release is concentrated, and the implosion is easily caused, so that the performance of the material is reduced. The temperature required by curing is relatively low, the time required by curing is long, curing is slow, and particularly, the epoxy resin composition has high requirements on the preparation process, low production efficiency and high cost. Therefore, it is very critical to obtain an epoxy resin composition suitable for the temperature required for curing and the time required for curing in order to achieve both quality and productivity.

Disclosure of Invention

Based on this, the main object of the present invention is to provide a composite curing agent and an epoxy resin composition prepared from the same. The epoxy resin composition prepared by using the composite curing agent provided by the invention as the curing agent has proper temperature and time required by curing reaction, and can give consideration to both the quality and the production benefit of the epoxy resin composition.

The specific technical scheme comprises the following steps:

the composite curing agent comprises a modified amine curing agent, an organic hydrazide and a Lewis acid-amine complex.

In one embodiment, the mass ratio of the modified amine curing agent, the organic hydrazide and the lewis acid-amine complex is (2.5-3.5) to (0.5-1.5): (0.5 to 1.5).

In one embodiment, the modified amine curing agent is an aliphatic amine curing agent.

In one embodiment, the aliphatic amine curing agent is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

In one embodiment, the organic hydrazide is selected from at least one of sebacic acid dihydrazide, adipic acid dihydrazide, terephthalic acid dihydrazide, and isophthalic acid hydrazide.

In one embodiment, the lewis acid amine complex is selected from at least one of boron trifluoride amine complex and boron trichloride amine complex.

In one embodiment, the boron trifluoride amine complex is selected from at least one of boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, and boron trifluoride-triethanolamine complex; or/and the boron trichloride amine complex is boron trichloride-octylamine complex.

The epoxy resin composition is prepared from raw materials including epoxy resin, a curing agent, an accelerator and a solvent, wherein the curing agent is the composite curing agent.

In one embodiment, the epoxy resin composition is prepared from the following raw materials in parts by mass:

in one embodiment, the epoxy resin is selected from at least one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an aliphatic glycidyl ether epoxy resin, and a glycidyl ester type epoxy resin.

In one embodiment, the accelerator is selected from urea amine accelerators.

In one embodiment, the urea amine accelerator is selected from at least one of N-p-chlorophenyl-N, N-dimethyl urea (chlorourea), N- (3, 4-dichlorophenyl) -N, N-dimethyl urea, N- (3-phenyl) -N, N-dimethyl urea, N- (4-phenyl) -N, N-dimethyl urea, 2-methylimidazolium urea, and thiourea.

In one embodiment, the solvent is at least one selected from acetone, butanone and propylene glycol methyl ether.

In one embodiment, the raw materials for preparing the epoxy resin composition further comprise an ambient temperature stabilizer.

In one embodiment, the ambient temperature stabilizer is at least one selected from the group consisting of alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and phenyl glycidyl ether.

The preparation method of the epoxy resin composition comprises the following steps: mixing the above raw materials.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, a modified amine curing agent, an organic hydrazide and a Lewis acid-amine complex compound are matched to form a compound curing agent formula, and the epoxy resin composition prepared by using the modified amine curing agent as a curing agent has the curing temperature of 120 ℃, the required complete curing time is controlled to be 8-12 min, the curing temperature of 150 ℃, the required complete curing time is controlled to be 5-10 min, the required temperature and the required time for the curing reaction are appropriate, the curing efficiency is not reduced, and the curing reaction is mild, so that the problems of large reaction heat release, explosive polymerization, large brittleness after curing molding, low bending strength, poor size stability and the like caused by violent reaction are effectively avoided. The curing agent is used as a preparation raw material, can be mixed with epoxy resin, an accelerant and a solvent to prepare the epoxy resin composition, and has the advantages of simple process and high production benefit.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The embodiment of the invention provides a composite curing agent which comprises a modified amine curing agent, an organic hydrazide and a Lewis acid-amine complex.

The addition of the modified amine can increase the glass transition temperature of the cured resin and increase the heat resistance, and the obtained intermediate-temperature fast-curing epoxy resin composition has better storage stability.

The curing temperature of the Lewis acid-amine complex is about 120 ℃, which is consistent with the curing temperature of the organic hydrazide after the carbamide amine accelerator is used.

The organic hydrazide is an epoxy resin latent curing agent and has good storage stability, but the curing temperature is high, generally 150-170 ℃, the curing temperature can be reduced to 120 ℃ by adding the urea amine accelerant, and energy is rapidly accumulated in the process of carrying out rapid curing reaction on the organic hydrazide and the resin, so that the curing reaction of the modified amine, the Lewis acid amine complex and the resin is stimulated. By matching and using various curing agents with different activities, the reaction heat release during rapid curing can be effectively slowed down, and the rapid curing of the resin can be realized.

Preferably, the mass ratio of the modified amine curing agent, the organic hydrazide and the lewis acid-amine complex is (2.5-3.5) to (0.5-1.5): (0.5 to 1.5).

Preferably, the modified amine curing agent is an aliphatic amine curing agent. More preferably, the aliphatic amine-based curing agent is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

Preferably, the organic hydrazide is selected from at least one of sebacic acid dihydrazide, adipic acid dihydrazide, terephthalic acid dihydrazide and isophthalic acid hydrazide.

Preferably, the lewis acid amine complex is at least one selected from the group consisting of boron trifluoride amine complex and boron trichloride amine complex. It is to be understood that the specific types of boron trifluoride amine complexes and boron trichloride amine complexes are not particularly limited in the embodiments of the present invention, and for example, boron trifluoride amine complexes may be boron trifluoride-piperidine complexes, boron trifluoride-monoethylamine complexes, boron trifluoride-triethanolamine complexes, etc., and boron trichloride amine complexes may be boron trichloride-octylamine complexes, etc.

The embodiment of the invention also provides an epoxy resin composition, the preparation raw materials of the epoxy resin composition comprise epoxy resin, a curing agent, an accelerant and a solvent, and the curing agent is the composite curing agent.

Preferably, the epoxy resin composition is prepared from the following raw materials in parts by mass:

preferably, the epoxy resin is at least one selected from the group consisting of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an aliphatic glycidyl ether epoxy resin, and a glycidyl ester type epoxy resin.

Preferably, the accelerator is carbamidine accelerator. Further preferably, the urea amine accelerator is at least one selected from the group consisting of N-p-chlorophenyl-N, N-dimethyl urea (chlorourea), N- (3, 4-dichlorophenyl) -N, N-dimethyl urea, N- (3-phenyl) -N, N-dimethyl urea, N- (4-phenyl) -N, N-dimethyl urea, 2-methylimidazolium urea, and thiourea. The urea amine accelerator has the following functions: on the premise of not exceeding the storage life and the service performance of the organic hydrazide, the curing temperature is reduced and can be reduced to about 120 ℃.

Preferably, the solvent is at least one of acetone, butanone and propylene glycol methyl ether.

Preferably, the raw materials for preparing the epoxy resin composition further comprise an ambient temperature stabilizer. The normal temperature stabilizer is added, so that the epoxy resin and the curing agent can be prevented from reacting at normal temperature, and the storage stability is improved. It can be understood that, in order to achieve the improvement of the normal temperature stabilizing effect, a proper amount of a proper kind of normal temperature stabilizer can be added, for example, 0.5 to 5 parts by mass of the normal temperature stabilizer is added to the raw materials for preparing the epoxy resin composition, so as to form the following formula:

the kind of the room temperature stabilizer may be alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, or the like.

Embodiments of the present invention also relate to a method of preparing an epoxy resin composition as described above, the method comprising the steps of: mixing the above raw materials.

Example 1:

adding 9 parts of ethylenediamine modified curing agent, 3 parts of adipic acid dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 2:

adding 9 parts of ethylenediamine modified curing agent, 3 parts of adipic acid dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 70 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 3:

adding 9 parts of ethylenediamine modified curing agent, 3 parts of adipic acid dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 80 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 4:

adding 12 parts of ethylenediamine modified curing agent, 4 parts of adipic acid dihydrazide, 4 parts of boron trichloride-octylamine complex, 4 parts of 2-methylimidazolium urea and 150 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 5:

adding 12 parts of ethylenediamine modified curing agent, 4 parts of adipic acid dihydrazide, 4 parts of boron trichloride-octylamine complex, 4 parts of 2-methylimidazolium urea and 150 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 70 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 6:

adding 12 parts of ethylenediamine modified curing agent, 4 parts of adipic acid dihydrazide, 4 parts of boron trichloride-octylamine complex, 4 parts of 2-methylimidazolium urea and 150 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 80 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 7:

adding 18 parts of ethylenediamine modified curing agent, 6 parts of adipic acid dihydrazide, 6 parts of boron trichloride-octylamine complex, 6 parts of 2-methylimidazolium urea and 200 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 8:

adding 18 parts of ethylenediamine modified curing agent, 6 parts of adipic acid dihydrazide, 6 parts of boron trichloride-octylamine complex, 6 parts of 2-methylimidazolium urea and 200 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 70 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 9:

adding 18 parts of ethylenediamine modified curing agent, 6 parts of adipic acid dihydrazide, 6 parts of boron trichloride-octylamine complex, 6 parts of 2-methylimidazolium urea and 200 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 80 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 10:

adding 15 parts of ethylenediamine modified curing agent, 5 parts of adipic acid dihydrazide, 2 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 150 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 11:

adding 9 parts of ethylenediamine modified curing agent, 3 parts of adipic acid dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Example 12

Adding 12.5 parts of diethylenetriamine, 7.5 parts of sebacic dihydrazide, 7.5 parts of boron trifluoride-piperidine complex, 5 parts of thiourea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the mixture is completely dissolved, adding 60 parts of bisphenol F type epoxy resin and 0.5 part of butyl glycidyl ether after the mixture is completely dissolved, and uniformly stirring to prepare glue solution.

Example 13

Adding 21 parts of tetraethylenepentamine, 3 parts of isophthalic acid hydrazide, 3 parts of boron trifluoride-triethanolamine, 2 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of glycidyl ester type epoxy resin and 5 parts of ethylene glycol diglycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare a glue solution.

Comparative example 1:

adding 12 parts of adipic acid dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the mixture is completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the mixture is completely dissolved, and uniformly stirring to prepare glue solution.

Comparative example 2:

adding 12 parts of ethylenediamine modified curing agent, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the mixture is completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the mixture is completely dissolved, and uniformly stirring to prepare glue solution.

Comparative example 3:

adding 3 parts of ethylenediamine modified curing agent, 12 parts of adipic acid dihydrazide, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the materials are completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the materials are completely dissolved, and uniformly stirring to prepare glue solution.

Comparative example 4

This comparative example is that of example 1, the main difference with respect to example 1 being the use of a lewis acid instead of the lewis acid amine complex, as follows:

9 parts of ethylenediamine modified curing agent, 3 parts of adipic acid dihydrazide, 3 parts of boron trichloride, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent are added into a batching bottle and stirred by a stirrer until the materials are completely dissolved, and after the materials are completely dissolved, 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether are added and stirred uniformly to prepare glue solution.

Comparative example 5

This comparative example is that of example 1, and the main difference with respect to example 1 is that an acid anhydride curing agent is used instead of a modified amine curing agent, as follows:

9 parts of hexahydrophthalic anhydride (HHPA), 3 parts of adipic dihydrazide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent are added into a batching bottle and stirred by a stirrer until the mixture is completely dissolved, and after the mixture is completely dissolved, 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether are added and stirred uniformly to prepare glue solution.

Comparative example 6

This comparative example is that of example 1, the main difference with respect to example 1 being the use of dicyandiamide instead of the organic hydrazide, as follows:

adding 9 parts of ethylenediamine modified curing agent, 3 parts of dicyandiamide, 3 parts of boron trichloride-octylamine complex, 3 parts of 2-methylimidazolium urea and 100 parts of propylene glycol methyl ether solvent into a batching bottle, stirring until the mixture is completely dissolved, adding 60 parts of bisphenol A epoxy resin and 1 part of alkylene glycidyl ether after the mixture is completely dissolved, and uniformly stirring to prepare glue solution.

Performance detection

Firstly, reaction enthalpy of glue: DSC.

Secondly, complete curing time: after impregnation, the PP is baked for a certain time in an oven at 120 ℃/150 ℃ and then DSC is used for testing the time corresponding to the difference value between TG1 and TG2 being less than 5.

And thirdly, storage stability at 25 ℃: the gum or PP was left at 25 ℃ for a constant duration of reaction enthalpy.

TABLE 1

TABLE 2

	Example 8	Example 9	Example 10	Example 11
					Bisphenol A epoxy resin	70	80	60	60
Ethylene diamine modified curing agent	18	18	15	9
					Adipic acid dihydrazide	6	6	5	3
Boron trichloride-octylamine complex	6	6	2	3
					2-methylimidazolium urea	6	6	3	3
Alkylene glycidyl ethers	1	1	1	0
					Propylene glycol methyl ether	200	200	150	100
Glue reactionEnthalpy (g/J)	148	157	160	174
					Complete curing time (min) at 120 DEG C	8.7	9.1	9.2	10.1
Complete curing time (min) at 150 DEG C	5.5	6.0	6.1	7.2
					Heat resistance (S)	>300	>300	>300	>300
Storage stability at 25 ℃ (d)	≥30	≥30	≥30	<20

TABLE 3

TABLE 4

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.