Preparation method of basalt fiber / organic boron compound modified epoxy resin flame-retardant composite material

Abstract

The invention relates to the technical field of flame-retardant materials, in particular to a preparation method of a basalt fiber / organic boron compound modified epoxy resin flame-retardant composite material, which is characterized by comprising 30 to 50 parts of basalt fiber, 10 to 20 parts of organic boron compound, 50 to 80 parts of epoxy resin and 1 to 5 parts of additive, according to the composite material, by adding the basalt fiber and the organic boron compound, the flame retardant property of the epoxy resin is greatly improved, the basalt fiber has excellent heat resistance, the organic boron compound has excellent carbonization capacity, and water can be generated in the heating process to reduce combustion heat, so that the flame retardant effect is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of flame retardant materials, and in particular to a method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material. Background Art

[0002] Epoxy resin, a thermosetting resin, is widely used in aerospace, coatings, adhesives, and electronic packaging due to its excellent mechanical and electrochemical properties. However, epoxy resin is highly flammable and can easily cause fires when exposed to open flames in air. It also releases large amounts of smoke and toxic gases, endangering people's lives and property. Therefore, the development of epoxy resin materials with high flame retardancy is a research priority.

[0003] With growing environmental awareness, halogenated flame retardants are being phased out due to their toxicity and pollution issues. Boron-based flame retardants are gaining popularity due to their high efficiency, halogen-free, and environmentally friendly properties. Meanwhile, basalt fiber, due to its high strength, chemical resistance, high temperature resistance, electrical insulation, and fire resistance, is gaining popularity in the construction, petrochemical, automotive, and marine industries. Therefore, combining basalt fiber / organoboron compounds with epoxy resin can improve the flame retardancy of epoxy resin. Summary of the Invention

[0004] The object of the present invention is to provide a method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The basalt fiber / organoboron compound modified epoxy resin flame retardant composite material comprises the following components:

[0007] 30-50 parts of basalt fiber,

[0008] 10 to 20 parts of an organic boron compound,

[0009] 50-80 parts of epoxy resin,

[0010] 1 to 5 parts of additives,

[0011] Preferably, the organic boron compound is at least one of phenylboronic acid, 4-vinylphenylboronic acid, and 4-carboxylphenylboronic acid.

[0012] Preferably, the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol P epoxy resin.

[0013] Preferably, the additive is at least one of a curing agent, a compatibilizer, and an antioxidant; the curing agent is an alkaline curing agent; the compatibilizer is SEBS maleic anhydride grafted; and the antioxidant is antioxidant 1010.

[0014] Preferably, the specific steps of the preparation are:

[0015] A1: Weigh the organoboron compound, epoxy resin, and additives in proportion and mix thoroughly in a high-speed mixer to obtain a resin matrix;

[0016] A2: The resin matrix prepared in step (A1) is melted and impregnated with the basalt fiber to ensure good bonding between the fiber and the resin, and then cured using a flat vulcanizer to obtain a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material.

[0017] Preferably, in step A1, the stirring speed is 4000-8000 r / min, and the stirring time is 0.5-2 h.

[0018] Preferably, in step A2, the curing temperature is 120-190° C., the curing pressure is 10-30 MPa, and the curing time is 10-30 min.

[0019] The present invention has the following advantages and beneficial effects:

[0020] (1) The basalt fiber / organoboron compound modified epoxy resin flame retardant composite material of the present invention is simple to prepare, low in cost, and environmentally friendly.

[0021] (2) The basalt fiber / organoboron compound modified epoxy resin flame retardant composite material of the present invention utilizes the synergistic flame retardant effect of basalt fiber and organoboron compound, and can achieve excellent flame retardant properties even with a relatively small addition amount.

[0022] (3) The basalt fiber / organoboron compound modified epoxy resin flame retardant composite material of the present invention also has excellent mechanical properties. DETAILED DESCRIPTION

[0023] For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.

[0024] Example 1

[0025] A basalt fiber / organoboron compound modified epoxy resin flame-retardant composite material comprises the following components: 30 parts basalt fiber, 10 parts phenylboric acid, 80 parts bisphenol A epoxy resin, 2 parts ethylenediamine, 1 part SEBS maleic anhydride grafted resin, and 1 part antioxidant 1010. The basalt fiber has excellent high-temperature resistance, chemical corrosion resistance, and mechanical strength, and can provide effective support and reinforcement in high-temperature environments. The basalt fiber used in the present invention is a pre-treated fiber, and the surface treatment helps to enhance its bonding with the resin matrix; phenylboric acid, as an organoboron compound, has good carbonization ability and can effectively improve the flame-retardant properties of the composite material. The water vapor generated by its decomposition reaction at high temperature can dilute the oxygen concentration in the combustion environment, thereby slowing the combustion process; bisphenol A epoxy resin is a common epoxy resin with good thermosetting properties, mechanical strength, and chemical stability, and is suitable for applications requiring high strength and high-temperature resistance. Its excellent bonding properties strengthen the bond between the resin and basalt fiber, enhancing the overall performance of the composite. Ethylenediamine, as a curing agent, undergoes a cross-linking reaction with the epoxy resin, accelerating the curing process and increasing the resin's hardness and heat resistance. The addition of ethylenediamine also helps improve the material's mechanical properties and thermal stability. The SEBS maleic anhydride grafting agent exhibits excellent compatibility, improving the bond between the resin matrix and the basalt fiber, thereby enhancing the composite's mechanical properties and thermal stability. Antioxidant 1010 effectively inhibits the resin's oxidation reaction at high temperatures, extending the composite's service life and improving its thermal stability.

[0026] A method for preparing a basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material includes weighing phenylboric acid, bisphenol A epoxy resin, ethylenediamine, SEBS maleic anhydride grafting agent, and antioxidant 1010 in appropriate proportions and stirring them in a high-speed mixer at 6000 rpm for 0.5 h. After uniform mixing, a resin matrix is ​​obtained. During this process, all components are ensured to be evenly mixed, ensuring that each component in the resin matrix is ​​fully dispersed and agglomeration is avoided. After stirring, samples are taken to check for uniformity and to ensure that there are no undissolved particles in the resin matrix. Subsequently, the resin matrix is ​​melted and impregnated with the basalt fiber for composite impregnation. Prior to addition, the basalt fiber is pretreated to remove surface impurities and ensure good wettability in the molten resin. Curing is performed on a flat-plate vulcanizer at a temperature of 150°C, a pressure of 10 MPa, and a time of 30 min. These curing pressure and temperature settings help ensure sufficient cross-linking of the resin, a tight bond between the basalt fiber and the resin matrix, and improved mechanical properties of the composite material. A basalt fiber / organoboron compound modified epoxy resin flame retardant composite material is obtained.

[0027] Example 2

[0028] A basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material comprises the following components: 30 parts basalt fiber, 15 parts 4-vinylphenylboronic acid, 80 parts bisphenol A epoxy resin, 3 parts 2-methylimidazole, 1 part SEBS maleic anhydride grafted compound, and 1 part antioxidant 1010. The vinyl groups in 4-vinylphenylboronic acid copolymerize with the epoxy resin, strengthening the resin's crosslinking structure and thereby improving the material's mechanical properties and thermal stability. 2-methylimidazole accelerates the epoxy resin's curing reaction, particularly at lower temperatures, exhibiting a strong catalytic effect. It effectively promotes the crosslinking reaction between epoxy groups and amino compounds, thereby increasing the resin's curing speed and crosslinking density.

[0029] A method for preparing a basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material includes weighing 4-vinylphenylboronic acid, bisphenol A epoxy resin, 2-methylimidazole, SEBS maleic anhydride grafted thereto, and antioxidant 1010 in appropriate proportions and stirring them in a high-speed mixer at 6000 rpm for 0.5 h. After uniform mixing, a resin matrix is ​​obtained. The resin matrix is ​​then melted and impregnated with the basalt fiber, and then cured on a flat-plate vulcanizer at a temperature of 150°C, a pressure of 10 MPa, and a curing time of 30 minutes to obtain the basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material.

[0030] Example 3

[0031] A basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material comprises the following components: 30 parts basalt fiber, 10 parts 4-carboxyphenylboronic acid, 80 parts bisphenol A epoxy resin, 3 parts triethylenetetramine, 1 part SEBS maleic anhydride grafted compound, and 1 part antioxidant 1010. The carboxyl groups in the 4-carboxyphenylboronic acid react with the epoxy resin, increasing the crosslinking density and thus improving the thermal stability and mechanical strength of the composite material. Triethylenetetramine reacts with the epoxy groups in the epoxy resin, accelerating the curing reaction. It has a high reaction rate and effectively catalyzes the crosslinking of the epoxy resin at both room and elevated temperatures.

[0032] A method for preparing a basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material includes weighing 4-carboxylphenylboronic acid, bisphenol A epoxy resin, triethylenetetramine, SEBS maleic anhydride grafted thereto, and antioxidant 1010 in appropriate proportions and stirring them in a high-speed mixer at 6000 rpm for 0.5 hours until uniformly mixed to obtain a resin matrix. The resin matrix is ​​then melted and impregnated with the basalt fiber, and then cured on a flat-plate vulcanizer at a temperature of 150°C, a pressure of 10 MPa, and a curing time of 30 minutes to obtain the basalt fiber / organoboron compound-modified epoxy resin flame-retardant composite material.

[0033] Examples 4-6

[0034] The differences from Examples 1-3 are that 80 parts of bisphenol A epoxy resin are replaced with 80 parts of bisphenol F epoxy resin. Bisphenol F epoxy resin excels in terms of higher thermal stability and lower volatility, making it suitable for more demanding environmental conditions. The curing temperature is set from 150°C to 160°C. This change helps improve the efficiency of the curing process and further enhances the strength and high-temperature resistance of the composite material.

[0035] Examples 7-9

[0036] The difference from Example 1-3 is that 80 parts of bisphenol A epoxy resin are replaced with 80 parts of bisphenol S epoxy resin. Bisphenol S epoxy resin has a higher heat deformation temperature and stronger mechanical properties, and is suitable for high temperature and high strength application environments.

[0037] Examples 10-12

[0038] The difference from Examples 1-3 is that 80 parts of bisphenol A epoxy resin are replaced with 80 parts of bisphenol P epoxy resin, which has better electrical insulation properties. The curing time is set from 30 minutes to 20 minutes. This adjustment improves production efficiency and shortens the production cycle while ensuring the performance of the composite material.

[0039] The flame retardant properties of the basalt fiber / organoboron compound modified epoxy resin flame retardant composite materials prepared in Examples 1-12 were tested using a vertical combustion tester in accordance with ASTM D3801. The test results are shown in Table 1.

[0040] Table 1

[0041] serial number Flame retardant grade Example 1 V-0 Example 2 V-0 Example 3 V-0 Example 4 V-0 Example 5 V-0 Example 6 V-0 Example 7 V-0 Example 8 V-0 Example 9 V-0 Example 10 V-0 Example 11 V-0 Example 12 V-0

[0042] The above description is only a preferred embodiment of the present invention, which certainly cannot be used to limit the scope of rights of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and changes can be made without departing from the principles of the present invention. These improvements and changes are also considered to be within the scope of protection of the present invention.

Claims

1. A method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material, characterized by: 30-50 parts of basalt fiber, 10-20 parts of organic boron compound, 50-80 parts of epoxy resin, and 1-5 parts of additives.

2. The method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to claim 1, characterized in that: The organic boron compound is at least one of phenylboronic acid, 4-vinylphenylboronic acid, and 4-carboxylphenylboronic acid.

3. The method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to claim 1, characterized in that: The epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol P epoxy resin.

4. The method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to claim 1, characterized in that: The additive is at least one of a curing agent, a compatibilizer, and an antioxidant. The curing agent is an alkaline curing agent, the compatibilizer is SEBS maleic anhydride grafted, and the antioxidant is antioxidant 1010.

5. A method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to any one of claims 1 to 4, characterized in that: (1) An organic boron compound, epoxy resin and additives are weighed in proportion and thoroughly mixed in a high-speed mixer to obtain a resin matrix. (2) melting the resin matrix prepared in step (1) and impregnating and compounding it with basalt fiber, and curing it through a flat vulcanizer to obtain a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material.

6. The method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to claim 5, characterized in that: In step (1), the stirring speed is 4000-8000 r / min, and the stirring time is 0.5-2 h.

7. The method for preparing a basalt fiber / organoboron compound modified epoxy resin flame retardant composite material according to claim 5, characterized in that: In step (2), the curing temperature is 120-190° C., the curing pressure is 10-30 MPa, and the curing time is 10-30 min.