Flame-retardant epoxy silsesquioxane resin condensate and preparation method thereof

Abstract

The invention relates to a flame-retardant epoxy silsesquioxane resin condensate, and belongs to the field of flame-retardant materials. The epoxy silsesquioxane resin is prepared from the following raw materials in parts by weight: 50-75 parts of epoxy silsesquioxane, 15-35 parts of a diluent and 10-15 parts of a curing agent. The invention also discloses a preparation method of the flame-retardant epoxy silsesquioxane cured resin, which comprises the following steps: uniformly mixing epoxy silsesquioxane, the diluent and the curing agent, injecting into a glass plate mold, and curing to obtain the flame-retardant epoxy silsesquioxane cured resin. The preparation method is mild in condition, easy to control and suitable for expanded production. And the epoxy silsesquioxane alkyl resin with excellent flame retardant effect and mechanical property can be prepared without adding any flame retardant.

Description

Technical Field

[0001] The invention relates to a flame retardant epoxy silsesquioxane resin cured product and a preparation method thereof, belonging to the field of flame retardant materials. Background Art

[0002] Bisphenol A epoxy resin has excellent heat resistance, chemical corrosion resistance and electrical insulation, and is widely used in aerospace, building materials and military fields. However, bisphenol A epoxy resin has high viscosity and requires high processing temperature. In addition, bisphenol A epoxy resin has low flame retardancy and is easily ignited when exposed to fire. During the combustion process, it will quickly release a large amount of heat, smoke and toxic gases such as CO and CO2, which is not conducive to its further development in cutting-edge fields.

[0003] Epoxy silsesquioxane has good thermal stability, low toxicity and smoke suppression. By adding a diluent to reduce the viscosity of epoxy silsesquioxane, problems such as high viscosity and high processing temperature can be effectively solved.

[0004] The flame-retardant epoxy silsesquioxane resin cured product prepared by room temperature curing has excellent flame retardancy, low smoke release and good mechanical properties, which can meet its application in cutting-edge fields. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a flame retardant epoxy silsesquioxane resin cured product having excellent flame retardancy, low smoke release and good mechanical properties.

[0006] The objectives of the present invention are achieved through the following technical solutions.

[0007] The present invention is a flame retardant epoxy silsesquioxane resin cured product and a preparation method thereof. The specific implementation steps are as follows:

[0008] A flame retardant epoxy silsesquioxane-based resin cured product comprises the following raw materials in parts by weight: 50 to 75 parts of epoxy silsesquioxane, 15 to 35 parts of a diluent, and 10 to 15 parts of a curing agent.

[0009] The epoxy silsesquioxane monomer structural formula is as follows:

[0010]

[0011] The diluent is one or a mixture of 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, C12-14 fatty glycidyl ether, polypropylene glycol diglycidyl ether, n-octanol glycidyl ether, o-cresol glycidyl ether and trimethylolpropane glycidyl ether.

[0012] The curing agent is one or a mixture of isophorone diamine, metaphenylenediamine, metaxylene diamine, tetramethyl diamino octadiene, pyromellitic dianhydride and maleic anhydride.

[0013] The present invention also provides a method for preparing a flame retardant epoxy silsesquioxane resin cured product. The processing equipment used in the preparation method includes a vacuum pump, a vacuum drying oven and a glass plate mold. The preparation method includes the following steps:

[0014] (1) Stirring the epoxy silsesquioxane monomer represented by Formula I and the diluent at 20°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.

[0015] (2) Adding a curing agent to the epoxy silsesquioxane resin obtained in step (1) and stirring the mixture evenly.

[0016] (3) The epoxy silsesquioxane resin obtained in step (2) 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 20° C. and 60° 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.

[0017] (4) Injecting the epoxy silsesquioxane resin treated in step (3) into a laboratory-made glass plate mold.

[0018] (5) Curing the sample prepared in step (4) at 10-80° C. to obtain a flame retardant epoxy silsesquioxane resin cured product.

[0019] Beneficial Effects

[0020] The invention has low processing temperature, is easy to control, and is suitable for large-scale production and application. The prepared flame-retardant epoxy silsesquioxane resin cured product has excellent flame retardant performance, low smoke release and good mechanical properties.

[0021] 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.

[0022] Example 1

[0023] 1. 150 g of epoxy silsesquioxane monomer was dissolved in 45 g of 1,4-butanediol diglycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0024] 2. Add 30 g of isophorone diamine to the epoxy silsesquioxane resin obtained by mixing well, and stir well.

[0025] 3. The evenly stirred epoxy silsesquioxane resin is placed in a vacuum oven at a negative pressure of -0.09 MPa to remove bubbles until all the bubbles are removed.

[0026] 4. Inject the epoxy silsesquioxane resin after removing bubbles into the glass plate mold. Then cure the mold at 25° C. for 72 hours. After curing, take the sample out of the mold to obtain a flame retardant epoxy silsesquioxane resin cured product.

[0027] Example 2

[0028] 1. 105 g of epoxy silsesquioxane monomer was dissolved in 34 g of o-cresol glycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0029] 2. Add 22 g of pyromellitic dianhydride to the epoxy silsesquioxane resin obtained by mixing well, and stir well.

[0030] 3. The uniformly stirred epoxy silsesquioxane resin is placed in a vacuum oven at a negative pressure of -0.10 MPa to remove bubbles until all the bubbles are removed.

[0031] 4. Inject the epoxy silsesquioxane resin after removing bubbles into the glass plate mold. Then cure the mold at 60° C. for 12 hours. After curing, take the sample out of the mold to obtain a flame retardant epoxy silsesquioxane resin cured product.

[0032] Example 3

[0033] 1. 500 g of epoxy silsesquioxane monomer was dissolved in 170 g of trimethylolpropane glycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0034] 2. Add 110 g of m-xylene diamine to the epoxy silsesquioxane resin obtained by mixing well, and stir well.

[0035] 3. Place the evenly stirred epoxy silsesquioxane resin in a vacuum oven at a negative pressure of -0.08 MPa to remove bubbles until all the bubbles are removed.

[0036] 4. Inject the epoxy silsesquioxane resin after removing bubbles into the glass plate mold. Then cure the mold at 30° C. for 72 hours. After curing, take the sample out of the mold to obtain a flame retardant epoxy silsesquioxane resin cured product.

[0037] Example 4

[0038] 1. 70 g of epoxy silsesquioxane monomer was dissolved in 21 g of polypropylene glycol diglycidyl ether at 40° C. to obtain epoxy silsesquioxane resin.

[0039] 2. Add 15 g of tetramethyl diamino octadiene to the epoxy silsesquioxane resin obtained by mixing well, and stir well.

[0040] 3. The uniformly stirred epoxy silsesquioxane resin is placed in a vacuum oven at a negative pressure of -0.10 MPa to remove bubbles until all the bubbles are removed.

[0041] 4. Inject the epoxy silsesquioxane resin after removing bubbles into the glass plate mold. Then cure the mold at 50° C. for 24 hours. After curing, take the sample out of the mold to obtain a flame retardant epoxy silsesquioxane resin cured product.

[0042] The flame retardant epoxy silsesquioxane resin cured products obtained in Examples 1 to 4 were tested for oxygen index, cone calorimeter, smoke density and flexural strength. 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:

[0043] Table 1

[0044]

[0045]

[0046] It can be seen from Table 1 that the flame retardant epoxy silsesquioxane-based resin cured products prepared in Examples 1 to 4 have a higher oxygen index, lower heat release and smoke release, and excellent flexural strength.

[0047] 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 flame retardant epoxy silsesquioxane resin cured product, characterized in that: The method comprises the following raw materials in parts by weight: 50 to 75 parts of epoxy silsesquioxane, 15 to 35 parts of diluent and 10 to 15 parts of curing agent.

2. A flame retardant epoxy silsesquioxane resin cured product according to claim 1, characterized in that: The structural formula of the epoxysilsesquioxane monomer used is as follows:

3. The flame retardant epoxy silsesquioxane resin cured product according to claim 1, characterized in that: The diluent used is one or a mixture of 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, C12-14 fatty glycidyl ether, polypropylene glycol diglycidyl ether, n-octanol glycidyl ether, o-cresol glycidyl ether and trimethylolpropane glycidyl ether.

4. A flame retardant epoxy silsesquioxane resin cured product according to claim 1, characterized in that: The curing agent used is one or a mixture of isophorone diamine, metaphenylenediamine, metaxylene diamine, tetramethyl diamino octadiene, pyromellitic dianhydride and maleic anhydride.

5. A method for preparing a flame retardant epoxy silsesquioxane resin cured product according to any one of claims 1 to 4, characterized in that: The processing equipment used in the preparation method includes a vacuum pump, a vacuum drying oven, and a glass plate mold. The preparation method includes the following steps: (1) stirring the epoxy silsesquioxane monomer represented by formula I and a diluent at 20° C. to 60° C. until the mixture is uniformly mixed to obtain an epoxy silsesquioxane resin; (2) adding a curing agent to the epoxy silsesquioxane resin obtained in step (1) and stirring evenly; (3) removing bubbles from the epoxy silsesquioxane resin obtained in step (2) by negative pressure in a vacuum drying oven, wherein the temperature for removing bubbles is controlled between 20° C. and 60° 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; (4) injecting the epoxy silsesquioxane resin treated in step (3) into a glass plate mold; (5) Curing the sample prepared in step (4) at 10-80° C. to obtain a flame retardant epoxy silsesquioxane resin cured product.

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