An epoxy resin composition and a method for producing the same

Abstract

The application discloses an epoxy resin composition and a preparation method thereof, and the preparation method comprises the following steps: uniformly stirring bisphenol F type epoxy resin, a plasticizer, a stabilizer, a curing agent and a modifier, then adding the mixture into a mold, curing at 90-120 DEG C for 20-50 minutes, then curing at 160-180 DEG C for 0.5-2 hours, and cooling to room temperature to obtain a product; the modifier comprises mica iron oxide; the epoxy resin curing system contains epoxy groups, hydroxyl groups and polar groups such as ether bonds, amine bonds and ester bonds, can not only generate electrostatic attraction with a phase interface, but also can react with free radicals on the surface of a medium to form chemical bonds, and can endow the epoxy curing product with extremely high adhesive strength; in the application, the bisphenol F type epoxy resin EPON862 is used as a base resin, has moderate viscosity, can uniformly disperse the mica iron oxide and nano titanium white powder, and can simultaneously improve the impact strength and near-infrared reflectivity of the product.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer material modification, and particularly relates to an epoxy resin composition and a preparation method thereof. BACKGROUND

[0002] Epoxy resin is a general term for compounds containing two or more than two epoxy groups in the molecular structure and capable of forming a three-dimensional network solidified product in the presence of appropriate chemical reagents, and is an important class of thermosetting resins. Epoxy resin includes not only oligomers with epoxy groups, but also low molecular compounds containing epoxy groups. As a resin matrix for adhesives, coatings and compositions, epoxy resin is widely used in water conservancy, transportation, machinery, electronics, home appliances, automobiles and aerospace fields.

[0003] Epoxy resin contains various polar groups and active epoxy groups, so it has strong adhesion to metals, glass, cement, wood, plastics and other polar materials, especially materials with high surface activity. At the same time, the cohesive strength of epoxy cured product is also very large, so the adhesive strength is very high. During the curing of epoxy resin, there is basically no low molecular volatile substance produced. The volume shrinkage rate of the adhesive layer is small, about 1% to 2%, which is one of the smallest varieties of thermosetting resins in terms of curing shrinkage. After adding fillers, it can be reduced to below 0.2%. The linear expansion coefficient of epoxy cured product is also very small. Therefore, the internal stress is small, which has little effect on the adhesive strength. The creep of epoxy cured product is small, and the dimensional stability is good. However, the epoxy resin composition is generally brittle, and the anti-peeling, anti-cracking and impact resistance are poor.

[0004] Infrared rays are one of the many invisible light rays in sunlight, also known as infrared thermal radiation, and have strong thermal effects. Infrared rays can be divided into three parts, namely near-infrared rays (high-frequency infrared rays, higher energy), medium-infrared rays (medium-frequency infrared rays, moderate energy) and far-infrared rays (low-frequency infrared rays, lower energy). Infrared rays (especially near-infrared rays) have a strong thermal effect, and objects irradiated by them will produce a significant thermal effect, resulting in a temperature rise.

[0005] The temperature of the surface of the epoxy resin material will rise to varying degrees when it is exposed to sunlight for a long time. Especially in summer, the surface of the material will feel hot to the touch. At present, the reflectivity of the resin to sunlight is often improved by adding additives that reflect sunlight in the resin, but these additives often cause the mechanical properties of the resin to deteriorate. How to provide an epoxy resin with high infrared reflectivity and good mechanical properties is a technical problem that needs to be solved urgently. SUMMARY

[0006] The purpose of the present application is to provide an epoxy resin composition and a preparation method thereof to solve the problems in the prior art.

[0007] The object of the present application is achieved by the following technical solutions.

[0008] The preparation method of the epoxy resin composition comprises the following steps:

[0009] After the bisphenol F type epoxy resin, the plasticizer, the stabilizer, the curing agent and the modifier are uniformly stirred, the mixture is added into a mold, and then the mixture is cured at 90-120 DEG C for 20-50 minutes and then cured at 160-180 DEG C for 0.5-2 hours, and the product is obtained after cooling to room temperature; the modifier comprises mica iron oxide, the mica iron oxide is flaky crystalline powder, and the particle size is 600-2000 mesh.

[0010] In a further aspect, the modifier further comprises titanium white powder, the titanium white powder is rutile titanium white powder, the average particle size is 0.05-10 microns, and the weight ratio of the titanium white powder to the mica iron oxide is (15-50):(25-80).

[0011] As a preferred technical solution, the epoxy equivalent weight of the bisphenol F type epoxy resin is 165-180 g / mol.

[0012] As a preferred technical solution, the plasticizer is dimethylphenyl dibutyl phosphate.

[0013] As a preferred technical solution, the stabilizer is diphenyl phosphite.

[0014] As a preferred technical solution, the curing agent is an amine curing agent; the amine curing agent is at least one of triethylene tetramine and ethylenediamine, and the two amine curing agents have fast curing speed and low viscosity.

[0015] The present application further provides an epoxy resin composition prepared by the preparation method.

[0016] Compared with the prior art, the present application has the beneficial effects of:

[0017] The epoxy resin curing system contains active epoxy groups, hydroxyl groups and polar groups such as ether bonds, amine bonds and ester bonds, which not only can generate electrostatic attraction with the adjacent interface, but also can react with the free radicals on the surface of the medium to form chemical bonds, thereby imparting the epoxy cured product with extremely high adhesive strength. In the present application, the bisphenol F type epoxy resin EPON862 is used as the base resin, and the viscosity is moderate, which can make the mica iron oxide and the nano titanium white powder uniformly dispersed, and the impact strength and the near-infrared reflectivity of the product are simultaneously improved.

[0018] The product has poor performance when the curing agent is phthalic anhydride, pyromellitic anhydride and other anhydride curing agents. When triethylenetetramine, ethylenediamine and other amine curing agents are selected, the impact resistance and near-infrared reflectivity of the product are obviously improved. DETAILED DESCRIPTION

[0019] The application will be further described below in conjunction with examples. Obviously, the described examples are part of the examples of the application, rather than all the examples. Based on the examples in the application, all other examples obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0020] The types and suppliers of the reagents used in the following examples and comparative examples are as follows:

[0021] Bisphenol F type epoxy resin EPON862, Shanghai Kaijin Chemical Co., Ltd.

[0022] The plasticizer is dibutyl phthalate, Jinan Run Tai Chemical Co., Ltd.

[0023] The stabilizer is diphenyl phosphite, Jinan Run Tai Chemical Co., Ltd.

[0024] The curing agent is triethylenetetramine and ethylenediamine, Shandong Duoli Chemical Co., Ltd.

[0025] The mica iron oxide is a flaky crystalline powder with a particle size of 800 mesh, Anhui Mingduo Protective Material Co., Ltd.

[0026] The titanium white powder is rutile titanium white powder with an average particle size of 0.1 μm, Ningbo Jixi Nano New Material Co., Ltd.

[0027] The above reagents are only used to illustrate the source and composition of the reagents used in the experiments of the application, so as to fully disclose, and do not mean that other similar reagents or other suppliers' reagents cannot achieve the application.

[0028] Example 1:

[0029] A preparation method of an epoxy resin composition, comprising the following steps:

[0030] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of ethylenediamine, 40 parts of mica iron oxide are uniformly stirred, added into a mold, cured at 100℃ for 35 minutes, cured at 175℃ for 1 hour, and the product is obtained after the mold is opened.

[0031] Example 2:

[0032] A preparation method of an epoxy resin composition, comprising the following steps:

[0033] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of triethylenetetramine, 70 parts of mica iron oxide, 45 parts of titanium white powder are stirred uniformly, added into the mold, cured at 100°C for 35 minutes, cured at 175°C for 1 hour, opened the mold to get the product.

[0034] Example 3:

[0035] A preparation method of an epoxy resin composition, comprising the following steps:

[0036] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of triethylenetetramine, 70 parts of mica iron oxide, 45 parts of titanium white powder are stirred uniformly, added into the mold, cured at 100°C for 35 minutes, cured at 175°C for 1 hour, opened the mold to get the product.

[0037] Example 4:

[0038] A preparation method of an epoxy resin composition, comprising the following steps:

[0039] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of triethylenetetramine, 70 parts of mica iron oxide, 45 parts of titanium white powder are stirred uniformly, added into the mold, cured at 100°C for 35 minutes, cured at 175°C for 1 hour, opened the mold to get the product.

[0040] Example 5:

[0041] A preparation method of an epoxy resin composition, comprising the following steps:

[0042] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of triethylenetetramine, 70 parts of mica iron oxide, 45 parts of titanium white powder are stirred uniformly, added into the mold, cured at 100°C for 35 minutes, cured at 175°C for 1 hour, opened the mold to get the product.

[0043] Example 6:

[0044] A preparation method of an epoxy resin composition, comprising the following steps:

[0045] 1000 parts of bisphenol F type epoxy resin, 55 parts of plasticizer, 48 parts of stabilizer, 90 parts of triethylenetetramine, 70 parts of mica iron oxide, 45 parts of titanium white powder are stirred uniformly, added into the mold, cured at 100°C for 35 minutes, cured at 175°C for 1 hour, opened the mold to get the product.

[0046] Comparative Example 1 (compared with Example 5)

[0047] In this comparative example, bisphenol A type E51 epoxy resin is used to replace bisphenol F type epoxy resin in Example 5, and other technical parameters are the same.

[0048] Comparative Example 2 (compared with Example 5)

[0049] In this comparative example, the curing agent phthalic anhydride is used to replace the curing agent triethylenetetramine in Example 5 in equal amount, and other technical parameters are the same.

[0050] Comparative Example 3 (compared with Example 5)

[0051] In this comparative example, the curing agent pyromellitic anhydride is used to replace the curing agent triethylenetetramine in Example 5 in equal amount, and other technical parameters are the same.

[0052] Comparative Example 4 (compared with Example 5)

[0053] In this comparative example, the same amount and particle size of red iron oxide is used to replace the mica iron oxide in Example 5, and other process parameters are the same.

[0054] Comparative Example 5 (compared with Example 5)

[0055] In this comparative example, the same amount and particle size of zinc oxide is used to replace the mica iron oxide in Example 5, and other process parameters are the same.

[0056] Comparative Example 6 (compared with Example 5)

[0057] In this comparative example, the same amount and particle size of zinc oxide is used to replace the titanium dioxide in Example 5, and other process parameters are the same.

[0058] Comparative Example 7 (compared with Example 5)

[0059] In this comparative example, no mica iron oxide is added, and the amount of titanium dioxide is 90 parts; other process parameters are the same as those in Example 5.

[0060] Performance test

[0061] The products prepared in each example and comparative example are tested for relevant performance according to the following method:

[0062] Simple beam notched impact strength test: the product is prepared into a simple beam notched impact sample, the sample size is 127mmx13mmx3.2mm, V-shaped notch, notch depth is 1 / 5; the notched impact strength test is tested according to ASTM D6110-2018.

[0063] Near-infrared reflectivity test: tested according to standard GB / T 25261-2018, in which the near-infrared reflectivity is the ratio of reflected and incident solar radiation energy flux in the near-infrared waveband of 780nm-2500nm.

[0064] The material surface temperature test standard is room temperature 23℃, relative humidity 50%, using infrared lamp tube irradiation for 30 minutes, irradiation distance 40cm.

[0065] The performance test results are shown in Table 1

[0066] Table 1 Performance test results

[0067] Test item Charpy notched impact strength (kJ / m 2 )]]> Near infrared reflectance % Surface temperature Example 1 21.5 44.8 33.1 Example 2 23.2 58.5 27.4 Example 3 22.6 64.1 24.8 Example 4 23.5 59.2 26.2 Example 5 26.2 63.3 24.9 Example 6 21.3 59.4 25.9 Comparative Example 1 17.6 40.8 35.4 Comparative Example 2 14.9 29.8 40.6 Comparative Example 3 15.5 31.2 39.9 Comparative Example 4 12.7 58.3 26.6 Comparative Example 5 12.3 28.6 41.3 Comparative Example 6 21.8 45.5 33.3 Comparative Example 7 18.8 34.1 38.4

[0068] The bisphenol F type epoxy resin EPON862 in the application is used as a base resin, has moderate viscosity, can make mica iron oxide and nano titanium white powder uniformly dispersed, and has excellent impact resistance and near-infrared reflectivity.

[0069] When the curing agent is an anhydride curing agent such as phthalic anhydride and pyromellitic anhydride, the product has poor performance.

[0070] As shown by Examples 5 and 6, the technical effect of adding 60 parts of mica iron oxide and 30 parts of titanium white powder is more excellent than that of adding 30 parts of mica iron oxide and 60 parts of titanium white powder.

[0071] The addition of mica iron oxide in the application can not only significantly increase the impact resistance of the base, but also increase the near-infrared light reflectivity of the base.

[0072] The above description of the examples is for the convenience of the ordinary skilled person in the art to understand and apply the application. Those skilled in the art can obviously easily make various modifications to these examples, and apply the general principles described herein to other examples without having to undergo creative labor. Therefore, the application is not limited to the examples herein, and the improvements and modifications made by those skilled in the art without departing from the scope of the application should be within the scope of protection of the application.

Claims

1. A method for producing an epoxy resin composition, characterized by: The method comprises the following steps: The bisphenol F type epoxy resin, plasticizer, stabilizer, curing agent and modifier are stirred uniformly, then added into a mold, cured at 90-120℃ for 20-50 minutes, then cured at 160-180℃ for 0.5-2 hours, and cooled to room temperature to obtain the product; the modifier comprises mica iron oxide The weight ratio of the bisphenol F type epoxy resin, plasticizer, stabilizer, curing agent and mica iron oxide is 1000: (50-100): (15-85): (50-150): (25-80); The modifier further comprises titanium white, and the weight ratio of the titanium white and mica iron oxide is (15-50): (25-80); The curing agent is an amine curing agent; the amine curing agent is at least one of triethylenetetramine and ethylenediamine.

2. The method for producing an epoxy resin composition according to claim 1, characterized by: The mica iron oxide is a flaky crystalline powder, and the particle size is 600-2000 mesh.

3. The method for preparing the epoxy resin composition according to claim 1, characterized in that: The titanium white is rutile titanium white, and the average particle size is 0.05-10 µm.

4. The method for preparing the epoxy resin composition according to claim 1, characterized in that: The epoxy equivalent weight of the bisphenol F type epoxy resin is 165-180 g / mol.

5. The method for preparing the epoxy resin composition according to claim 1, characterized in that: The plasticizer is dimethylphenyl dibutyl phosphate.

6. The method for preparing the epoxy resin composition according to claim 1, characterized in that: The stabilizer is diphenyl phosphite.

7. An epoxy resin composition characterized by: The epoxy resin composition is prepared according to the preparation method in any one of claims 1-6.