Degradable epoxy resin composite material and preparation method thereof

Abstract

The invention relates to a degradable epoxy resin composite material, and belongs to the technical field of high polymer materials. The technical scheme is as follows: the degradable epoxy resin composite material consists of the following components in parts by mass: 100 parts of bisphenol A epoxy resin; 5 to 20 parts of polycaprolactone; 1 to 5 parts of nano silicon dioxide; 40 to 50 parts of methyl tetrahydrophthalic anhydride; and 1 to 2 parts of 4-methyl-2-ethylimidazole. The preparation method has the beneficial effects that the epoxy resin is taken as a base material, degradable polymers including polycaprolactone (PCL) and nano silicon dioxide (SiO2) are doped through physical blending, and then a three-dimensional network structure is formed through chemical crosslinking, so that the mechanical strength of the epoxy resin material is improved, the degradability of the material is enhanced, the operation is simple, and the cost is low.

Description

Technical Field

[0001] This invention relates to a biodegradable epoxy resin composite material and its preparation method, belonging to the field of polymer materials technology. Background Technology

[0002] Epoxy resins are a widely used class of polymer materials with excellent physicochemical properties, but they also have drawbacks such as high brittleness and difficulty in degradation. While there is considerable research on preparing epoxy resin composites to improve their mechanical properties through physical blending and chemical modification, studies on degradability mainly focus on the costly chemical modification approach. Research on physical blending, on the other hand, primarily focuses on expanding the application scenarios and enhancing the performance of epoxy resin materials. For example, Chinese patent application CN202411161273.4 describes the preparation of a degradable epoxy resin material by blending a chemically modified degradable imide-based hyperbranched epoxy resin with a traditional bisphenol A type epoxy resin followed by lamination and curing; Chinese patent application CN202510294306.0 describes the preparation of a modified epoxy resin prepolymer through chemical modification, followed by blending and curing to obtain a type of degradable epoxy resin material; and Chinese patent application CN202510382466.0 describes the preparation of a degradable epoxy resin composition by adding degradation aids to epoxy resin material components and then using a physical blending-chemical crosslinking method. To improve the mechanical properties of epoxy resin composites, blending with inorganic particles or reinforcing materials is generally adopted. For example, Chinese patent application CN202610144147.0 studied the preparation of composite materials by blending epoxy resin with multi-sized silica and applied them to ultrasonic transducers; Chinese patent application CN202511988658.2 studied the preparation of basalt fiber epoxy resin composites and the improvement of their mechanical properties and weather resistance.

[0003] There is an urgent need in this field to study an epoxy resin composite material that can improve the mechanical strength of epoxy resin materials through physical blending while also enhancing the biodegradability of the materials. Summary of the Invention

[0004] The purpose of this invention is to provide a biodegradable epoxy resin composite material and its preparation method. Using epoxy resin as the matrix material, biodegradable polymer polycaprolactone (PCL) and nano-silica (SiO2) are incorporated through physical blending, and then a three-dimensional network structure is formed through chemical crosslinking. This improves the mechanical strength of the epoxy resin material while enhancing its biodegradability, thus solving the aforementioned problems in the prior art.

[0005] The technical solution of this invention is:

[0006] A biodegradable epoxy resin composite material, comprising the following components by weight:

[0007] 100 parts of bisphenol A type epoxy resin;

[0008] 5-20 parts of polycaprolactone;

[0009] 1-5 parts of nano-silica;

[0010] 40-50 parts of methyltetrahydrophthalic anhydride;

[0011] 1-2 parts of 4-methyl-2-ethylimidazole.

[0012] A method for preparing a biodegradable epoxy resin composite material, comprising the following specific steps:

[0013] (1) After the mold is fixed, brush it with dimethyl silicone oil and preheat it in an oven at 90 ℃;

[0014] (2) Weigh 100 parts of bisphenol A epoxy resin by weight using an electronic balance, add the corresponding amount of polycaprolactone and nano silica according to the proportion, and heat and stir in a constant temperature water bath at 90 ℃ for 30-35 min using a heat-collecting constant temperature magnetic stirrer.

[0015] (3) After stirring, add the corresponding amount of 4-methyl-2-ethylimidazole and methyltetrahydrophthalic anhydride according to the proportion, stir by hand at room temperature for 3-4 minutes, stir evenly and pour into a preheated mold and place in an oven.

[0016] (4) Dry at 90 °C for 2 hours, then transfer to 130 °C for 2 hours, and then cure at 150 °C for 1 hour until drying is complete, to obtain a biodegradable epoxy resin composite material.

[0017] The beneficial effects of this invention are as follows: using epoxy resin as the matrix material, biodegradable polymer polycaprolactone (PCL) and nano-silica (SiO2) are incorporated through physical blending, and then a three-dimensional network structure is formed through chemical cross-linking. This improves the mechanical strength of the epoxy resin material while enhancing its biodegradability. The operation is simple and the cost is low. Detailed Implementation

[0018] The present invention will be further described below with reference to embodiments:

[0019] A biodegradable epoxy resin composite material, comprising the following components by weight:

[0020] 100 parts of bisphenol A type epoxy resin;

[0021] 5-20 parts of polycaprolactone;

[0022] 1-5 parts of nano-silica;

[0023] 40-50 parts of methyltetrahydrophthalic anhydride;

[0024] 1-2 parts of 4-methyl-2-ethylimidazole.

[0025] A method for preparing a biodegradable epoxy resin composite material, comprising the following specific steps:

[0026] (1) After the mold is fixed, brush it with dimethyl silicone oil and preheat it in an oven at 90 ℃;

[0027] (2) Weigh 100 parts of bisphenol A epoxy resin by weight using an electronic balance, add polycaprolactone and nano silica in proportion, and heat and stir in a constant temperature water bath at 90 ℃ for 30-35 min using a heat-collecting constant temperature magnetic stirrer.

[0028] (3) After stirring, add 4-methyl-2-ethylimidazole and methyltetrahydrophthalic anhydride in proportion, stir by hand at room temperature for 3-4 minutes, stir evenly and pour into a preheated mold and place in an oven;

[0029] (4) Dry at 90 °C for 2 hours, then transfer to 130 °C for 2 hours, and then cure at 150 °C for 1 hour until drying is complete, to obtain a biodegradable epoxy resin composite material.

[0030] In a specific embodiment, the main instruments are as follows:

[0031] Table 1. Names, models, and manufacturers of the main instruments and equipment used in the experiment.

[0032]

[0033] In this embodiment, the sample formulations in Table 2 were prepared by fixing the amount of epoxy resin (EP), adjusting the amount of polycaprolactone (PCL), and varying the proportion and amount of oleophilic nano-SiO2 of different sizes.

[0034] Table 2 Composite Material Formulation

[0035]

[0036] Adjust the proportions of different strips according to the ratios in Table 2.

[0037] (1) Fix the mold with screws, brush it with dimethyl silicone oil, and put the fixed mold into an oven at 90 ℃ for preheating.

[0038] (2) By mass, 100 parts of epoxy resin were weighed using an electronic balance for sample 3, and 15 parts of PCL and 1 part of oleophilic nano-SiO2 were added; 100 parts of epoxy resin were weighed using an electronic balance for sample 4, and 15 parts of PCL and 3 parts of oleophilic nano-SiO2 were added; 100 parts of epoxy resin were weighed using an electronic balance for sample 5, and 15 parts of PCL and 5 parts of oleophilic nano-SiO2 were added; each sample was heated and stirred for 30-35 min in a constant temperature water bath at 90 ℃ using a heat-collecting constant temperature magnetic stirrer.

[0039] (3) After stirring, add 1.44 parts of 4-methyl-2-ethylimidazole and 44 parts of methyltetrahydrophthalic anhydride to samples 3-5 respectively, stir by hand at room temperature for 3-4 minutes, stir evenly and pour into the corresponding positions of the preheated molds and place in the oven.

[0040] (4) Prepare blank control sample 1 and sample 2. For sample 1, add only 100 parts epoxy resin, 1 part lipophilic nano SiO2, and 1.44 parts 4-methyl-2-ethylimidazolium and 44 parts methyltetrahydrophthalic anhydride weighed in advance. For sample 2, add only 100 parts epoxy resin, and 1.44 parts 4-methyl-2-ethylimidazolium and 44 parts methyltetrahydrophthalic anhydride weighed in advance. The stirring time and operation method are the same as described above.

[0041] (5) Samples 1-5 were dried at 90 °C for 2 hours, then transferred to 130 °C for 2 hours and cured at 150 °C for 1 hour to form sample strips 1-5.

[0042] (6) After drying, take out samples 1-5, pack them in separate bags, and label and store them.

[0043] Experimental conclusions regarding the effects of different formulations on mechanical properties, including tensile strength and impact properties:

[0044] Table 3. Effects of different formulations on mechanical properties, including tensile strength and impact properties.

[0045]

[0046] Table 3 shows that, with EP, PCL, and other additives remaining constant, changing only the amount of nano-SiO2 leads to a decrease in both tensile strength and impact strength as the nano-SiO2 content increases. Considering tensile and impact strength and elongation at break, the optimal performance for the 100 nm SiO2 addition corresponds to sample #3 with a 100 / 15 / 1 ratio and an impact strength of 12.83 KJ. m -2 The tensile strength was 51.32 MPa. An epoxy resin material without physical blending under the same experimental conditions was used as a blank control, compared to the data from blank sample No. 2 (impact strength 4.68 KJ). m -2 The tensile strength was 30.50 MPa. The impact strength of the composite material increased to 274.14%, and the tensile strength increased to 168.26%. Furthermore, experimental results showed that the composite material underwent partial degradation.

Claims

1. A biodegradable epoxy resin composite material, characterized in that: By weight, it consists of the following components: 100 parts of bisphenol A type epoxy resin; 5-20 parts of polycaprolactone; 1-5 parts of nano-silica; 40-50 parts of methyltetrahydrophthalic anhydride; 1-2 parts of 4-methyl-2-ethylimidazole.

2. A method for preparing the biodegradable epoxy resin composite material according to claim 1, characterized in that, The specific steps include the following: (1) After the mold is fixed, brush it with dimethyl silicone oil and preheat it in an oven at 90 ℃; (2) Weigh 100 parts of bisphenol A epoxy resin by weight using an electronic balance, add the corresponding amount of polycaprolactone and nano silica according to the proportion, and heat and stir in a constant temperature water bath at 90 ℃ for 30-35 min using a heat-collecting constant temperature magnetic stirrer. (3) After stirring, add the corresponding amount of 4-methyl-2-ethylimidazole and methyltetrahydrophthalic anhydride according to the proportion, stir by hand at room temperature for 3-4 minutes, stir evenly and pour into a preheated mold and place in an oven. (4) Dry at 90 °C for 2 hours, then transfer to 130 °C for 2 hours, and then cure at 150 °C for 1 hour until drying is complete, to obtain a biodegradable epoxy resin composite material.

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