Glass fiber reinforced flame-retardant epoxy silsesquioxane resin composite material and preparation method thereof

Abstract

The invention relates to a glass fiber reinforced flame-retardant epoxy silsesquioxane resin composite material, and belongs to the field of polymer composite materials. The glass fiber reinforced epoxy silsesquioxane resin composite material is prepared from the following components in percentage by mass: 45%-70% of epoxy silsesquioxane resin, 25%-45% of glass fiber and 5%-10% of a curing agent. The invention also discloses a preparation method of the glass fiber reinforced flame-retardant epoxy silsesquioxane resin. The preparation method comprises the following steps: uniformly mixing the epoxy silsesquioxane resin and the curing agent, and pouring the epoxy silsesquioxane resin into the glass fiber under the action of negative pressure to obtain the glass fiber reinforced flame-retardant epoxy silsesquioxane resin. And curing to obtain the glass fiber reinforced flame-retardant epoxy silsesquioxane resin composite material. The glass fiber reinforced flame-retardant epoxy silsesquioxane resin composite material has excellent flame retardant property and mechanical property. And the preparation method is simple, and reaction conditions are mild.

Description

Technical Field

[0001] The invention relates to a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material and a preparation method thereof, belonging to the field of polymer composite materials. Background Art

[0002] Commercial epoxy resin has excellent thermal stability, corrosion resistance and weather resistance, and is widely used in aerospace, hull materials and electronic packaging. However, epoxy resin has a high viscosity and requires a high processing temperature. In addition, epoxy resin has low flame retardancy, with a limiting oxygen index value of only 20.5%. It is very easy to ignite, and releases a lot of heat, smoke and toxic gases during combustion, which limits its development in cutting-edge fields.

[0003] One of the most common methods to improve the flame retardancy of epoxy resin is to add flame retardants, but usually about 15wt% of flame retardants are needed to achieve a good flame retardant effect. After adding a large amount of flame retardants, the viscosity of the epoxy resin system increases significantly, making the processing and preparation of the subsequent samples more difficult.

[0004] Glass fiber has low cost and exhibits excellent heat resistance and mechanical reinforcement effect. At the same time, the interaction between glass fiber and epoxy silsesquioxane resin can effectively improve the flame retardant properties of glass fiber reinforced flame retardant epoxy silsesquioxane resin.

[0005] The epoxy silsesquioxane resin composite material prepared by glass fiber reinforced epoxy silsesquioxane resin has excellent flame retardant properties, low smoke release and high mechanical properties, making its application range in cutting-edge fields wider. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material with excellent flame retardant performance, low smoke release and high mechanical properties.

[0007] The objectives of the present invention are achieved through the following technical solutions.

[0008] The present invention is a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material and a preparation method thereof. The specific implementation steps are as follows:

[0009] A glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material comprises the following components in terms of mass percentage: 45%-70% epoxy silsesquioxane resin, 25%-45% glass fiber, and 5%-10% curing agent.

[0010] The epoxy silsesquioxane resin is prepared by mixing an epoxy silsesquioxane resin monomer and a diluent. The structural formula of the epoxy silsesquioxane resin monomer is shown in Formula I.

[0011] The diluent is one or a mixture of 1,4-butanediol diglycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, alkylene glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and o-cresyl glycidyl ether.

[0012] The glass fiber is E-type glass fiber.

[0013] The curing agent is isophorone diamine, 4,4-diaminodiphenyl sulfone, 4,4-diaminodiphenylmethane, dimethyl diamino octadiene, phthalic anhydride, trimellitic anhydride, or a mixture thereof.

[0014] The present invention also provides a method for preparing a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material. The processing equipment used in the preparation method includes a vacuum pump and a vacuum drying oven. The preparation method includes the following steps:

[0015] (1) The epoxy silsesquioxane resin monomer represented by Formula I and the diluent are stirred at 25° C. to 60° C. until they are uniformly mixed to obtain an epoxy silsesquioxane resin. The preferred mixing temperature is 40° C. to 50° C.

[0016] (2) Dry the glass fiber at 70°C-95°C to constant weight.

[0017] (3) Adding a curing agent to the epoxy silsesquioxane resin obtained in step (1) and stirring the mixture evenly.

[0018] (4) The epoxy silsesquioxane resin obtained in step (3) is placed in a vacuum drying oven to remove all bubbles in the epoxy silsesquioxane resin by using negative pressure. The temperature for removing bubbles is controlled between 25° C. and 40° C. The negative pressure used is controlled between -0.07 MPa and -0.10 MPa. The time for removing bubbles is until all bubbles are removed.

[0019] (5) Infusing the epoxy silsesquioxane resin treated in step (4) into the glass fiber under negative pressure. The negative pressure is controlled between -0.07 MPa and -0.10 MPa, and the infusion time is controlled between 40 min and 50 min.

[0020] (6) Curing the sample prepared in step (5) at 25° C.-80° C. to obtain a glass fiber reinforced epoxy silsesquioxane-based resin composite material.

[0021] Beneficial Effects

[0022] The invention has simple operation process, mild reaction conditions and is suitable for large-scale production and application. The prepared epoxy silsesquioxane resin composite material has excellent flame retardant performance, low smoke release and excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Formula 1 is the structural formula of the epoxy silsesquioxane resin monomer used in the implementation case:

[0024]

[0025] The present invention is described in detail below with reference to specific embodiments, but the embodiments are not intended to limit the protection scope of the present invention.

[0026] Example 1

[0027] 1. 600 g of epoxy silsesquioxane resin monomer was dissolved in 180 g of 1,4-butanediol diglycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0028] 2. Add 83 g of isophorone diamine to the above-mentioned epoxy silsesquioxane resin and stir evenly.

[0029] 3. After drying about 400 g of glass fiber at 85°C for 24 h, seal it in a mold with a negative pressure of -0.07 MPa to -0.10 MPa.

[0030] 4. The evenly stirred epoxy silsesquioxane resin is placed in a vacuum oven at 30°C and a negative pressure of -0.09 MPa to remove bubbles until all the bubbles are removed.

[0031] 5. The epoxy silsesquioxane resin after excluding bubbles is poured into the sealed mold in step 3 under negative pressure. The mold is then cured at 30° C. for 72 hours. After curing, the sample is taken out of the mold to obtain a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material.

[0032] Example 2

[0033] 1. 630 g of epoxysilsesquioxane resin monomer was dissolved in 189 g of butyl glycidyl ether at 40° C. to obtain epoxysilsesquioxane resin.

[0034] 2. Add 88 g of 4,4-diaminodiphenyl sulfone to the above-mentioned epoxy silsesquioxane resin and stir evenly.

[0035] 3. After drying the glass fiber with a mass of about 446 g at 85° C. for 24 h, the glass fiber was sealed in a mold with a negative pressure of -0.07 MPa to -0.10 MPa.

[0036] 4. The evenly stirred epoxy silsesquioxane resin is placed in a vacuum oven at 30°C and a negative pressure of -0.09 MPa to remove bubbles until all the bubbles are removed.

[0037] 5. The epoxy silsesquioxane resin after excluding bubbles is poured into the sealed mold in step 3 under negative pressure. The mold is then cured at 30° C. for 72 hours. After curing, the sample is taken out of the mold to obtain a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material.

[0038] Example 3

[0039] 1. 650 g of epoxy silsesquioxane resin monomer was dissolved in 195 g of o-cresyl glycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0040] 2. Add 92 g of phthalic anhydride to the above-mentioned epoxy silsesquioxane resin and stir evenly.

[0041] 3. After drying the glass fiber with a mass of about 467 g at 85° C. for 24 h, the glass fiber was sealed in a mold with a negative pressure of -0.07 MPa to -0.10 MPa.

[0042] 4. The evenly stirred epoxy silsesquioxane resin is placed in a vacuum oven at 30°C and a negative pressure of -0.09 MPa to remove bubbles until all the bubbles are removed.

[0043] 5. The epoxy silsesquioxane resin after excluding bubbles is poured into the sealed mold in step 3 under negative pressure. The mold is then cured at 30° C. for 72 hours. After curing, the sample is taken out of the mold to obtain a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material.

[0044] Example 4

[0045] 1. 700 g of epoxysilsesquioxane resin monomer was dissolved in 200 g of alkylene glycidyl ether at 40° C. to obtain epoxysilsesquioxane resin.

[0046] 2. Add 100 g of isophorone diamine to the above-mentioned epoxy silsesquioxane resin and stir evenly.

[0047] 3. After drying the glass fiber with a mass of about 525 g at 85° C. for 24 h, the glass fiber was sealed in a mold with a negative pressure of -0.07 MPa to -0.10 MPa.

[0048] 4. The evenly stirred epoxy silsesquioxane resin is placed in a vacuum oven at 30°C and a negative pressure of -0.09 MPa to remove bubbles until all the bubbles are removed.

[0049] 5. The epoxy silsesquioxane resin after excluding bubbles is poured into the sealed mold in step 3 under negative pressure. The mold is then cured at 30° C. for 72 hours. After curing, the sample is taken out of the mold to obtain a glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material.

[0050] The glass fiber reinforced flame retardant epoxy silsesquioxane resin composites prepared in Examples 1 to 4 were subjected to oxygen index, cone calorimeter, smoke density and flexural strength tests. The oxygen index test was conducted in accordance with GB / T 8924; the cone calorimeter test was conducted in accordance with ISO 5660, with a radiation power of 50kW / m 2 ; Smoke density test is in accordance with ISO 5659 standard; Resin casting bending strength test is in accordance with GB / T 2570-1995 standard. The test results are shown in Table 1:

[0051] Table 1

[0052]

[0053] It can be seen from Table 1 that the glass fiber reinforced flame retardant epoxy silsesquioxane-based resin composite materials prepared in Examples 1-4 have a higher oxygen index, lower heat release and smoke release, and higher flexural strength.

[0054] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material, characterized in that: The raw materials for preparing the composite material include the following components by mass percentage: 45%-70% of epoxy silsesquioxane resin, 25%-45% of glass fiber and 5%-10% of curing agent.

2. The glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material according to claim 1, characterized in that: The epoxy silsesquioxane resin used is prepared by mixing an epoxy silsesquioxane resin monomer and a diluent. The structural formula of the epoxy silsesquioxane resin monomer is shown in Formula I. The diluent used is one or a mixture of 1,4-butanediol diglycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, alkylene glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether.

3. The glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material according to claim 1, characterized in that: The glass fiber used is E-type glass fiber.

4. The glass fiber reinforced flame retardant epoxy silsesquioxane resin composite material according to claim 1, characterized in that: The curing agent used is isophorone diamine, 4,4-diaminodiphenyl sulfone, 4,4-diaminodiphenylmethane, dimethyl diamino octadiene, phthalic anhydride, trimellitic anhydride, or a mixture of the above.

5. The method for preparing a glass fiber reinforced flame retardant epoxy silsesquioxane-based resin composite material according to any one of claims 1 to 4, characterized in that: The processing equipment used in the preparation method includes a vacuum pump and a vacuum drying oven. The preparation method includes the following steps: (1) stirring the epoxy silsesquioxane resin monomer represented by formula (I) and a diluent at 15° C. to 70° C. until the mixture is uniformly mixed to obtain an epoxy silsesquioxane resin; (2) drying the glass fiber at 70°C-95°C to constant weight; (3) adding a curing agent to the epoxy silsesquioxane resin obtained in step (1) and stirring evenly; (4) removing bubbles from the vinyl ester resin using negative pressure in a vacuum drying oven, wherein the temperature for removing bubbles is controlled between 20° C. and 45° C., the negative pressure used is controlled between -0.07 MPa and -0.10 MPa, and the time for removing bubbles is until all bubbles are removed; (5) pouring the epoxy silsesquioxane resin treated in step (4) into the glass fiber under the action of negative pressure, wherein the negative pressure is controlled between -0.07 MPa and -0.10 MPa, and the pouring time is controlled between 40 min and 50 min; (6) Curing the sample prepared in step (5) at 25° C.-80° C. to obtain a glass fiber reinforced flame retardant epoxy silsesquioxane-based resin composite material.

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