A weather-resistant epoxy resin composite material and its preparation method

Abstract

The present invention discloses a weather-resistant epoxy resin composite material and a preparation method thereof. The weather-resistant epoxy resin composite material is prepared from the following components in parts by weight: 800-1000 parts of bisphenol A type E-51 epoxy resin; 80-100 parts of diethylenetriamine; 90-120 parts of epoxypropane benzyl ether; 1-15 parts of antioxidant; 2-5 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one; 2-5 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine. In the present invention, 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one and N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine are added and used as a compound weather-resistant agent, which can greatly increase the weather resistance of bisphenol A type epoxy resin and at the same time maintain relatively excellent mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the field of composite materials, and particularly relates to a weather-resistant epoxy resin composite material and a preparation method thereof. Background Art

[0002] Epoxy resin refers to the general name of a class of polymers containing more than two epoxy groups in the molecule. It is the polycondensation product of epichlorohydrin and bisphenol A or polyol. Due to the chemical activity of the epoxy group, it can be ring-opened with a variety of compounds containing active hydrogen and cured and crosslinked to form a network structure. Therefore, it is a thermosetting resin. Bisphenol A type epoxy resin not only has the largest output and the most complete varieties, but also new modified varieties are constantly increasing and the quality is constantly improving. The characteristics of the epoxy resin injection molding process are that it changes the multiple sets of molds required for traditional mass production, can better control the exothermic reaction, realizes single-person single-machine and pipeline-type sealed closed-loop operation, improves the working environment and reduces the labor intensity.

[0003] In recent years, the application of epoxy resin has gradually expanded from indoor to outdoor, and is widely used in the laying of landscape roads, floor, bridges, building composite material reinforcement, etc. However, epoxy resin, especially bisphenol A type epoxy resin, has poor weather resistance, and its performance drops too fast after outdoor use. Summary of the Invention

[0004] The purpose of the present invention is to provide a weather-resistant epoxy resin composite material and a preparation method thereof to solve the problems in the prior art.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] A weather-resistant epoxy resin composite material is prepared from the following components in parts by weight:

[0007]

[0008] As a preferred technical solution, the epoxy equivalent of the bisphenol A type E-51 epoxy resin is 184-194, and the hydrolyzable chlorine wt% ≤ 0.1%; the antioxidant is antioxidant BHT.

[0009] The present invention also discloses a preparation method of the above-mentioned weather-resistant epoxy resin composite material, and the steps are as follows: Mix 800-1000 parts of bisphenol A type E-51 epoxy resin, 80-100 parts of diethylenetriamine, 90-120 parts of epoxypropane benzyl ether, 1-15 parts of antioxidant, 2-5 parts of 2,2'-(1,4-phenylene) bis-4H-3,1-benzoxazin-4-one, and 2-5 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl) oxalyl diamine evenly to obtain a mixture, and inject the mixture into a mold by an injection machine for curing to obtain the weather-resistant epoxy resin composite material. Further, the front section of the barrel temperature of the injection machine is 70-80°C, the rear section is 80-90°C, and the nozzle temperature is 90-100°C; the injection pressure of the injection machine is 20-30 Mpa. The curing includes two stages, namely: the first stage is cured at a temperature of 80-100°C for 1-3 h, and the second stage is cured at a temperature of 140-160°C for 1-2 h.

[0010] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0011] The curing process of epoxy resin is quite complex, and with the progress of photooxidation and thermal oxidation reactions, it makes the study of its aging phenomenon more complex and difficult. Generally speaking, under long-term light exposure, the amine-containing part in the epoxy resin molecule is oxidized into a chromophore containing a conjugated system, and the molecular chain of the ether-containing part is broken. In the present invention, 2,2'-(1,4-phenylene) bis-4H-3,1-benzoxazin-4-one and N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl) oxalyl diamine are added to the epoxy resin composite material as a compound weather-resistant agent, which can greatly delay and reduce the occurrence of the above-mentioned aging and degradation conditions, greatly increase the weather resistance of bisphenol A type epoxy resin, and at the same time can maintain a relatively excellent mechanical property. Specific embodiments

[0012] The following further describes the present invention in conjunction with embodiments. The following embodiments are only for illustrating the present invention rather than limiting it.

[0013] All raw materials in the examples and comparative examples are commercially available.

[0014] Among them, the bisphenol A type E-51 epoxy resin is CYD-128 of Baling Petrochemical; the manufacturer of diethylenetriamine is Jinan Chuangshi Chemical Industry; the manufacturer of epoxypropane benzyl ether is Shandong Suihua Biotechnology; the antioxidant is antioxidant BHT, and the manufacturer is Guangzhou Taosheng Chemical Co., Ltd.; the manufacturer of 2,2'-(1,4-phenylene) bis-4H-3,1-benzoxazin-4-one is Cyanamid of the United States; the manufacturer of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl) oxalyl diamine is Clariant.

[0015] The material property tests of each example and comparative example were carried out under the following conditions:

[0016] Tensile strength test: Conducted according to ISO 527-2 standard, the specimen size was 170*10*4 mm, and the tensile speed was 50 mm / min;

[0017] Flexural strength test: Conducted according to ISO 178 standard, the specimen size was 80*10*4 mm, the flexural speed was 2 mm / min, and the span was 64 mm;

[0018] Izod impact strength test of simply supported beam with notch: Conducted according to ISO 179-1 standard, the specimen size was 80*10*1 mm, and the sample preparation method was molding;

[0019] Weather resistance test: The tensile spline was subjected to ultraviolet accelerated aging (ultraviolet aging conditions are shown in Table 1), and its tensile strength and impact resistance were tested.

[0020] Table 1. Ultraviolet aging conditions

[0021]

[0022] Example 1

[0023] 800 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 90 parts of propylene oxide benzyl ether, 1 part of antioxidant, 2 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one, and 2 parts of N-(2-ethylphenyl)-N′-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine were mixed evenly, and the resulting mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 70 °C, the temperature of the rear section was 80 °C, the nozzle temperature was 90 °C, and the injection pressure was 30 Mpa. The mixture was injected into a mold using the injection molding machine for curing, cured at 80 °C for 1 hour, cured at 140 °C for 2 hours, the mold was opened, and the product was taken out.

[0024] Example 2

[0025] 900 parts of bisphenol A type E-51 epoxy resin, 90 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, 3 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one, and 3 parts of N-(2-ethylphenyl)-N′-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine were mixed evenly, and the resulting mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 80 °C, the temperature of the rear section was 90 °C, the nozzle temperature was 90 °C, and the injection pressure was 25 Mpa. The mixture was injected into a mold using the injection molding machine for curing, cured at 90 °C for 2 hours, cured at 150 °C for 2 hours, the mold was opened, and the product was taken out.

[0026] Example 3

[0027] Add the mixture obtained by uniformly mixing 1000 parts of bisphenol A type E-51 epoxy resin, 100 parts of diethylenetriamine, 120 parts of propylene oxide benzyl ether, 15 parts of antioxidant, 5 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one, and 5 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine into an injection molding machine. The temperature of the front section of the barrel of the injection molding machine is 80 °C, the temperature of the rear section is 90 °C, the temperature of the nozzle is 100 °C, and the injection pressure is 20 Mpa. Use the injection molding machine to inject the mixture into the mold for curing, cure at 100 °C for 3 hours, cure at 160 °C for 1 hour, open the mold, and take out the product.

[0028] Example 4

[0029] Add the mixture obtained by uniformly mixing 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, 4 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one, and 4 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine into an injection molding machine. The temperature of the front section of the barrel of the injection molding machine is 80 °C, the temperature of the rear section is 90 °C, the temperature of the nozzle is 100 °C, and the injection pressure is 20 Mpa. Use the injection molding machine to inject the mixture into the mold for curing, cure at 80 °C for 3 hours, cure at 160 °C for 2 hours, open the mold, and take out the product.

[0030] Comparative Example 1 (compared with Example 4)

[0031] Add the mixture obtained by uniformly mixing 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, and 8 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one into an injection molding machine. The temperature of the front section of the barrel of the injection molding machine is 80 °C, the temperature of the rear section is 90 °C, the temperature of the nozzle is 100 °C, and the injection pressure is 20 Mpa. Use the injection molding machine to inject the mixture into the mold for curing, cure at 80 °C for 3 hours, cure at 160 °C for 2 hours, open the mold, and take out the product.

[0032] Comparative Example 2 (compared with Example 4)

[0033] Add the mixture obtained by uniformly mixing 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, and 8 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine into an injection molding machine. The temperature of the front section of the barrel of the injection molding machine is 80 °C, the temperature of the rear section is 90 °C, the temperature of the nozzle is 100 °C, and the injection pressure is 20 Mpa. Use the injection molding machine to inject the mixture into the mold for curing, cure at 80 °C for 3 hours, cure at 160 °C for 2 hours, open the mold, and take out the product.

[0034] Comparative Example 3 (compared with Example 4)

[0035] 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, and 8 parts of n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate were mixed evenly, and the mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 80°C, the temperature of the rear section was 90°C, the nozzle temperature was 100°C, the injection pressure was 20 Mpa, and it was cured at 80°C for 3 hours and at 160°C for 2 hours. The mixture was injected into a mold by the injection molding machine for curing, the mold was opened, and the product was taken out.

[0036] Comparative Example 4 (compared with Example 4)

[0037] 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, and 8 parts of light stabilizer GW-628 were mixed evenly, and the mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 80°C, the temperature of the rear section was 90°C, the nozzle temperature was 100°C, the injection pressure was 20 Mpa, and the mixture was injected into a mold by the injection molding machine for curing. It was cured at 80°C for 3 hours and at 160°C for 2 hours, the mold was opened, and the product was taken out.

[0038] Comparative Example 5 (compared with Example 4)

[0039] 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, 4 parts of light stabilizer UV531, and 4 parts of light stabilizer UV327 were mixed evenly, and the mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 80°C, the temperature of the rear section was 90°C, the nozzle temperature was 100°C, the injection pressure was 20 Mpa, and the mixture was injected into a mold by the injection molding machine for curing. It was cured at 80°C for 3 hours and at 160°C for 2 hours, the mold was opened, and the product was taken out.

[0040] Comparative Example 6 (compared with Example 4)

[0041] 900 parts of bisphenol A type E-51 epoxy resin, 80 parts of diethylenetriamine, 100 parts of propylene oxide benzyl ether, 5 parts of antioxidant, 4 parts of light stabilizer 944, and 4 parts of light stabilizer 770 were mixed evenly, and the mixture was added to an injection molding machine. The temperature of the front section of the injection molding machine barrel was 80°C, the temperature of the rear section was 90°C, the nozzle temperature was 100°C, the injection pressure was 20 Mpa, and the mixture was injected into a mold by the injection molding machine for curing. It was cured at 80°C for 3 hours and at 160°C for 2 hours, the mold was opened, and the product was taken out.

[0042] The physical properties of the products obtained in each example and comparative example were detected respectively, and their performances are shown in Table 2:

[0043] Table 2 Test Results of Material Properties Obtained from Each Example and Comparative Example

[0044]

[0045]

[0046] As can be seen from the results of the above examples, adding 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one and N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyldiamine as a compound weathering agent in the present invention can greatly improve the weather resistance of bisphenol A epoxy resin, and at the same time can maintain a relatively excellent mechanical property.

[0047] These examples are only used to illustrate the present invention and should not limit the scope of the present invention. In addition, after reading the content of the present invention, those skilled in the art make various equivalent changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims of this application.

Claims

1. A weather-resistant epoxy resin composite material, characterized in that: Prepared from the following components in parts by weight:

2. The weather-resistant epoxy resin composite material according to claim 1, characterized in that: The epoxy equivalent of the bisphenol A type E-51 epoxy resin is 184-194, and the hydrolyzable chlorine wt% ≤ 0.1%.

3. The weather-resistant epoxy resin composite material according to claim 1, characterized in that: The antioxidant is antioxidant BHT.

4. The preparation method of the weather-resistant epoxy resin composite material according to any one of claims 1-3, characterized in that: The steps are as follows: Mix 800-1000 parts of bisphenol A type E-51 epoxy resin, 80-100 parts of diethylenetriamine, 90-120 parts of epoxypropane benzyl ether, 1-15 parts of antioxidant, 2-5 parts of 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one, and 2-5 parts of N-(2-ethylphenyl)-N'-(2-ethoxy-5-tert-butylphenyl)oxalyl diamine evenly to obtain a mixture, and inject the mixture into a mold using an injection machine for curing to obtain a weather-resistant epoxy resin composite material.

5. The preparation method of the weather-resistant epoxy resin composite material according to claim 4, characterized in that: The front section of the barrel temperature of the injection machine is 70-80 °C, the rear section is 80-90 °C, and the nozzle temperature is 90-100 °C; the injection pressure of the injection machine is 20-30 Mpa.

6. The preparation method of the weather-resistant epoxy resin composite material according to claim 4, characterized in that: The curing includes two stages, namely: the first stage is cured at a temperature of 80-100 °C for 1-3 h, and the second stage is cured at a temperature of 140-160 °C for 1-2 h.

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