1. A two-component epoxy resin composition is characterized by comprising a resin component and a curing component;

the resin component includes: epoxy resin, a toughening agent and a release agent;

the curing component comprises: anhydride curing agents, curing accelerators;

wherein the anhydride curing agent is one or more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, nadic anhydride and maleic anhydride;

the curing accelerator is one or more of thorium acetylacetonate, chromium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate and manganese acetylacetonate.

2. The two-component epoxy resin composition of claim 1, wherein the toughening agent is one or more of polypropylene glycol diglycidyl ether, linoleic acid dimer diglycidyl ester, epoxidized polybutadiene resin, and polysulfide rubber.

3. The two-part epoxy resin composition according to claim 1, wherein the release agent is one or more of zinc stearate, barium stearate, calcium stearate, lead stearate, and magnesium stearate.

4. The two-component epoxy resin composition according to claim 1, wherein the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, novolac epoxy resin, and silicone epoxy resin.

5. The two-component epoxy resin composition according to claim 1, wherein the epoxy resin composition comprises, in parts by weight,

the resin component includes: 100 parts of epoxy resin, 5-25 parts of toughening agent and 1-5 parts of release agent;

the curing component comprises: 80-100 parts of anhydride curing agent and 0.5-5 parts of curing accelerator.

6. The two-component epoxy resin composition according to claim 5, wherein the epoxy resin composition comprises, in parts by weight,

the resin component includes: 100 parts of epoxy resin, 10-15 parts of toughening agent and 1-3 parts of release agent;

the curing component comprises: 80-90 parts of anhydride curing agent and 0.5-2 parts of curing accelerator.

7. A method of preparing the two-part epoxy resin composition of claims 1-6, comprising the steps of:

uniformly mixing epoxy resin, a toughening agent and a release agent to obtain a resin component;

and (3) uniformly mixing the anhydride curing agent and the curing accelerator to obtain the curing component.

8. The method for preparing a two-part epoxy resin composition according to claim 7, wherein the step of uniformly mixing the acid anhydride curing agent and the curing accelerator comprises the steps of: and adding the curing accelerator into the anhydride curing agent, and uniformly stirring at a rotating speed of 500-1500 r/min.

9. The method for preparing a two-part epoxy resin composition according to claim 8, wherein the step of uniformly mixing the acid anhydride curing agent and the curing accelerator comprises the steps of: adding the curing accelerator into the anhydride curing agent, stirring for 20-30 min at 500-800 r/min, increasing the rotating speed to 1000-1500 r/min, and stirring for 10-20 min.

10. The method for preparing a two-component epoxy resin composition according to claim 9, wherein the method further comprises the following steps of, after the acid anhydride curing agent and the curing accelerator are uniformly mixed: and (3) preserving the heat of the uniformly mixed curing components at 80-90 ℃ for 40-60 min, and naturally cooling.

Background

Epoxy resin is a thermosetting polymer material with good adhesion, electrical insulation and chemical stability, is used as a resin matrix of an adhesive, a coating, a composite material and the like, and is widely applied to the fields of buildings, machinery, electronics and electricity, aerospace and the like. When the epoxy resin is used, a curing agent is required to be added, and the curing reaction is carried out under certain conditions to generate a product with a three-dimensional network structure, so that various excellent performances can be shown, and the epoxy resin becomes an epoxy material with real use value.

Epoxy resin curing agents can be classified into polyamine type, acid anhydride type, phenol type, polythiol type, and the like according to their chemical structures. The anhydride curing agent has the advantages of small irritation to skin and long service life. When it is used as curing agent, the cured epoxy resin has excellent mechanical performance and thermodynamic performance, especially excellent dielectric performance compared with amine cured resin. When the epoxy matrix resin and the anhydride curing agent are subjected to crosslinking reaction, the reaction is completed only at a very high temperature due to high activation energy, a large amount of energy is wasted, and the production process requirement and the production cost are increased, so that a curing accelerator is required to be added in an epoxy resin curing system to reduce the activation energy of the reaction, improve the reaction rate and shorten the reaction time.

The metal complex is a latent accelerator which is very effective in an epoxy resin system using acid anhydride as a curing agent, and can be used in the curing system of acid anhydride and epoxy resin.

Chinese patent CN106009527A discloses an insulating resin for a low-temperature-resistant motor, and specifically discloses an insulating resin for a low-temperature-resistant motor, which comprises an epoxy resin composition, an anhydride curing agent and a latent accelerator; wherein the anhydride curing agent is methyl nadic anhydride, dodecenyl succinic anhydride, poly sebacic anhydride and elaeostearic anhydride; the latent accelerator is aluminum acetylacetonate or chromium acetylacetonate. According to the scheme, although the molecular chain strength can be improved, the insulating resin with high and low temperature impact resistance can be obtained. However, the insulating resin in the patent is a resin for perfusion, and needs to be prepared at present, the steps in the glue solution preparation process are complex and long in time, the production efficiency is low, great waste of manpower and material resources is caused, and the actual requirements of continuous production of large-scale enterprises cannot be met.

Therefore, a two-component epoxy resin composition for pultrusion, which has long storage and service life, is simple and easy to prepare, and can meet the actual requirements of continuous production of large-scale enterprises, is urgently needed.

Disclosure of Invention

The invention aims to provide a two-component epoxy resin composition to solve the problem that the epoxy resin composition in the prior art is short in storage and use period.

In order to solve the above problems, the present invention provides a two-component epoxy resin composition comprising a resin component and a curing component;

the resin component includes: epoxy resin, a toughening agent and a release agent;

the curing component comprises: anhydride curing agents, curing accelerators;

wherein the anhydride curing agent is one or more of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, nadic anhydride and maleic anhydride;

the curing accelerator is one or more of thorium acetylacetonate, chromium acetylacetonate, cobalt acetylacetonate, aluminum acetylacetonate and manganese acetylacetonate.

Preferably, the toughening agent is one or more of polypropylene glycol diglycidyl ether, linoleic acid dimer diglycidyl ester, epoxidized polybutadiene resin and polysulfide rubber.

Preferably, the release agent is one or more of zinc stearate, barium stearate, calcium stearate, lead stearate and magnesium stearate.

Preferably, the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, novolac epoxy resin and silicone epoxy resin.

Preferably, the two-component epoxy resin composition comprises the following resin components in parts by weight: 100 parts of epoxy resin, 5-25 parts of toughening agent and 1-5 parts of release agent; the curing component comprises: 80-100 parts of anhydride curing agent and 0.5-5 parts of curing accelerator.

Further preferably, the two-component epoxy resin composition comprises the following resin components in parts by weight: 100 parts of epoxy resin, 10-15 parts of toughening agent and 1-3 parts of release agent; the curing component comprises: 80-90 parts of anhydride curing agent and 0.5-2 parts of curing accelerator.

The invention also provides a preparation method of the two-component epoxy resin composition, which comprises the following steps:

uniformly mixing epoxy resin, a toughening agent and a release agent to obtain a resin component;

and (3) uniformly mixing the anhydride curing agent and the curing accelerator to obtain the curing component.

Preferably, the acid anhydride curing agent and the curing accelerator are uniformly mixed, and the method comprises the following steps: and adding the curing accelerator into the anhydride curing agent, and uniformly stirring at a rotating speed of 500-1500 r/min.

Further preferably, the acid anhydride curing agent and the curing accelerator are uniformly mixed, and the method comprises the following steps: adding the curing accelerator into the anhydride curing agent, stirring for 20-30 min at 500-800 r/min, increasing the rotating speed to 1000-1500 r/min, and stirring for 10-20 min.

Preferably, after the anhydride curing agent and the curing accelerator are uniformly mixed, the method further comprises the following steps: and (3) preserving the heat of the uniformly mixed curing components at 80-90 ℃ for 40-60 min, and naturally cooling.

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

(1) the two-component epoxy resin composition comprises a resin component and a curing component, wherein the resin component comprises: epoxy resin, a toughening agent and a release agent; the curing component comprises an anhydride curing agent and a curing accelerator. When the anhydride curing agent is methyl tetrahydrophthalic anhydride and the curing accelerator is manganese acetylacetonate, the d orbitals of manganese metal ions are not filled, and according to the theory of a crystal field, when the metal ions are surrounded by ligands, d electron clouds of the metal ions are deformed to generate crystal field stabilizing energy, so that the metal complex is stabilized. The manganese acetylacetonate complex is stable at room temperature or lower temperatures in the form of a complex. During the curing reaction, the complex can form a transition state with acid anhydride along with the increase of the curing reaction temperature, and then catalyze the epoxy resin to perform alternate curing reaction to form an epoxy resin cured product with ester bonds as a cross-linked network. Because manganese metal ions in the complex have d-vacant orbitals, can be complexed with active functional groups such as epoxy groups or acid anhydrides, and limits the random reaction of the system, a system cured product has excellent dielectric properties and heat resistance at high and low temperatures, and when the complex is prepared into a composite fiber material, the obtained product has excellent mechanical properties.

(2) The toughening agent of the two-component epoxy resin composition is one or more of polypropylene glycol diglycidyl ether, linoleic acid dimer diglycidyl ester, epoxidized polybutadiene resin and polysulfide rubber. When the toughening agent is a mixture of polypropylene glycol diglycidyl ether and linoleic acid dimer diglycidyl ester, the obtained composition has optimal comprehensive performance when being prepared into glue solution and composite fiber materials. The mixture contains a large number of flexible chain segments, and the flexible chain segments can be embedded into a crosslinking network in the crosslinking process of the curing agent and the epoxy resin to generate micro phase separation and form a compact and loose alternate two-phase network structure, so that the dispersion of the internal stress of the material is facilitated, and the optimal effect is finally achieved.

Detailed Description

Those not indicated in the examples of the present invention were carried out under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The raw materials used in the examples are all commercially available.

Example 1

The two-component epoxy resin composition of the embodiment comprises a resin component and a curing component, and the resin component comprises the following components in parts by weight: 100 parts of epoxy resin, 5 parts of toughening agent and 3 parts of release agent;

the curing component comprises: 100 parts of anhydride curing agent and 0.5 part of curing accelerator.

Wherein the epoxy resin is novolac epoxy resin;

the toughening agent is epoxidized polybutadiene resin;

the release agent is lead stearate;

the anhydride curing agent is nadic anhydride;

the curing accelerator is thorium acetylacetonate.

The preparation method of the two-component epoxy resin composition comprises the following steps:

uniformly mixing epoxy resin, a toughening agent and a release agent to obtain a resin component;

taking an anhydride curing agent and a curing accelerator, adding the curing accelerator into the anhydride curing agent, stirring for 20min at 500r/min, then increasing the rotating speed to 1000r/min, stirring for 20min to obtain a curing component, preserving the temperature of the uniformly mixed curing component at 90 ℃ for 50min, and naturally cooling to obtain the product.

It should be noted that the two-component epoxy resin composition described in this embodiment is not exclusive in application, and those skilled in the art can be used for molding and processing of composite materials according to actual needs. In this embodiment, which is only an example, the two-component epoxy resin composition is used to prepare a fiber reinforced composite material, and the application method thereof is as follows:

and uniformly mixing the resin component and the curing component to obtain a glue solution, soaking a fiber material into the glue solution, and performing extrusion forming and curing to obtain the fiber reinforced composite material.

Example 2

The two-component epoxy resin composition of the embodiment comprises a resin component and a curing component, and the resin component comprises the following components in parts by weight: 100 parts of epoxy resin, 25 parts of toughening agent and 1 part of release agent;

the curing component comprises: 80 parts of anhydride curing agent and 5 parts of curing accelerator.

Wherein the epoxy resin is glycidyl ester type epoxy resin;

the toughening agent is linoleic acid dimer diglycidyl ester;

the release agent is calcium stearate;

the anhydride curing agent is tetrahydrophthalic anhydride;

the curing accelerator is aluminum acetylacetonate.

The preparation method of the two-component epoxy resin composition comprises the following steps:

uniformly mixing epoxy resin, a toughening agent and a release agent to obtain a resin component;

taking an anhydride curing agent and a curing accelerator, adding the curing accelerator into the anhydride curing agent, stirring for 30min at 800r/min, then increasing the rotating speed to 1300r/min, stirring for 10min to obtain a curing component, preserving the temperature of the uniformly mixed curing component for 60min at 85 ℃, and naturally cooling.

Example 3

The two-component epoxy resin composition of the embodiment comprises a resin component and a curing component, and the resin component comprises the following components in parts by weight: 100 parts of epoxy resin, 15 parts of toughening agent and 5 parts of release agent;

the curing component comprises: 90 parts of anhydride curing agent and 3.5 parts of curing accelerator.

Wherein the epoxy resin is bisphenol F type epoxy resin;

the toughening agent is polysulfide rubber;

the release agent is barium stearate;

the anhydride curing agent is hexahydrophthalic anhydride;

the curing accelerator is chromium acetylacetonate.

The preparation method of the two-component epoxy resin composition comprises the following steps:

uniformly mixing epoxy resin, a toughening agent and a release agent to obtain a resin component;

taking an anhydride curing agent and a curing accelerator, adding the curing accelerator into the anhydride curing agent, stirring for 25min at 650r/min, then increasing the rotating speed to 1500r/min, stirring for 15min to obtain a curing component, preserving the temperature of the uniformly mixed curing component at 90 ℃ for 40min, and naturally cooling.

Example 4

The two-component epoxy resin composition of the embodiment comprises a resin component and a curing component, and the resin component comprises the following components in parts by weight: 100 parts of epoxy resin, 15 parts of toughening agent and 3 parts of release agent;

the curing component comprises: 85 parts of anhydride curing agent and 1 part of curing accelerator.

Wherein the epoxy resin is bisphenol A type epoxy resin;

the toughening agent is linoleic acid dimer diglycidyl ester;

the release agent is zinc stearate;

the anhydride curing agent is methyl tetrahydrophthalic anhydride;

the curing accelerator is manganese acetylacetonate.

The two-component epoxy resin composition was prepared in the same manner as in example 1.

Example 5

The two-component epoxy resin composition of the embodiment comprises a resin component and a curing component, and the resin component comprises the following components in parts by weight: 100 parts of epoxy resin, 15 parts of toughening agent and 3 parts of release agent;

the curing component comprises: 85 parts of anhydride curing agent and 1 part of curing accelerator.

Wherein the epoxy resin is organic silicon epoxy resin;

the toughening agent is polypropylene glycol diglycidyl ether;

the release agent is magnesium stearate;

the anhydride curing agent is maleic anhydride;

the curing accelerator is cobalt acetylacetonate.

The two-component epoxy resin composition was prepared in the same manner as in example 1.

Example 6

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: replacing the anhydride curing agent with methyl tetrahydrophthalic anhydride by trimellitic anhydride.

Example 7

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: replacing the anhydride curing agent with methyl tetrahydrophthalic anhydride by methyl hexahydrophthalic anhydride.

Example 8

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: and replacing the curing accelerator with cobalt acetylacetonate from manganese acetylacetonate.

Example 9

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: and replacing the curing accelerator with aluminum acetylacetonate by manganese acetylacetonate.

Example 10

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: the toughening agent is replaced by the dimer diglycidyl linoleate into the polysulfide rubber.

Example 11

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: the toughening agent is replaced by polypropylene glycol diglycidyl ether by linoleic acid dimer diglycidyl ester.

Example 12

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: the toughening agent is prepared by mixing polypropylene glycol diglycidyl ether and linoleic acid dimer diglycidyl ester according to the weight ratio of 1: 1.

Comparative example 1

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: no curing accelerator was added.

Comparative example 2

This example provides a two-component epoxy resin composition, which uses the following raw materials and the preparation method completely the same as those in example 4, except that: no toughening agent was added.

Examples of Effect test

The two-component epoxy resin compositions prepared in examples 1 to 12 and comparative examples 1 to 2, numbered 1 to 14, were subjected to the following experiments, respectively:

(1) obtaining glue solution according to the using method in the embodiment 1, standing and storing the prepared glue solution at normal temperature (25 ℃), and counting the storage days; when the glue solution has gel phenomenon, the counting is stopped, and the result is used as the storage service life of the glue solution.

(2) And (3) soaking the fiber material in the prepared glue solution, and recording the pultrusion speed when the surface of the product has no crack, no die sticking and no unfilled corner in the pultrusion process.

(3) After pultrusion and curing, the fiber reinforced composite material is obtained, and samples are manufactured according to GB/T1447-.

Through determination, the following experimental results are obtained:

the results show that the manganese acetylacetonate complex exists stably in the form of the complex at room temperature, the storage and use period of the glue solution is prolonged, and the waste of manpower and material resources caused by glue preparation is greatly reduced. In the curing reaction process, the complex and the methyl tetrahydrophthalic anhydride can form a transition state along with the rise of the curing reaction temperature, then the epoxy resin is catalyzed to perform alternate curing reaction to form an epoxy resin cured product taking ester bonds as a cross-linked network, and the fiber reinforced composite material has excellent tensile strength and modulus performance. Meanwhile, the use of the toughening agent is combined, so that the obtained glue solution has long storage and use period, and the obtained composite fiber material has good mechanical properties. In particular, in example 12 in which polypropylene glycol diglycidyl ether and linoleic acid dimer diglycidyl ester were used in a composite manner, the obtained glue solution and fiber composite material had the best overall properties.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.