Flame-retardant modified basalt fiber, flame-retardant modified basalt fiber reinforced PET material and preparation method of flame-retardant modified basalt fiber reinforced PET material

Abstract

The invention relates to the technical field of flame-retardant modified materials, and discloses a flame-retardant modified basalt fiber, a flame-retardant modified basalt fiber reinforced PET (Polyethylene Terephthalate) material and a preparation method of the flame-retardant modified basalt fiber reinforced PET material. A halogen-free flame retardant is grafted on the surface of the basalt fiber to perform surface modification on the basalt fiber, and the halogen-free flame retardant is hydroquinone modified phenylphosphoryl dichloride. According to the technical scheme, the application of the FR-A in surface modification of the basalt fiber is creatively proposed for the first time, and by designing and optimizing the structure and connection mode of the FR-A and the basalt fiber, the material can form carbon at a relatively low temperature and is crosslinked with polymer material pyrolysis micromolecules at a high temperature to generate a carbon layer with high thermal stability; the candlewick effect inhibiting effect is good, the flame retardant property of the composite material can be further enhanced, and the mechanical property is considered.

Description

Technical Field

[0001] The invention relates to the technical field of flame retardant modified materials, and in particular to a flame retardant modified basalt fiber, a flame retardant modified basalt fiber reinforced PET material and a preparation method thereof. Background Art

[0002] As a new type of inorganic non-metallic material, basalt fiber (BF) has shown broad application prospects in many fields due to its unique physical and chemical properties. The advantages of basalt fiber are:

[0003] 1. High strength: The high strength of basalt fiber enables the composite material to exhibit excellent tensile and compressive properties when subjected to external loads.

[0004] 2. High temperature resistance: Basalt fiber has good heat resistance and can maintain a stable structure in high temperature environment, making it suitable for high temperature applications.

[0005] 3. High corrosion resistance: Basalt fiber has strong resistance to corrosive substances such as acids and alkalis, allowing the composite material to be used for a long time in harsh environments without being damaged.

[0006] 4. Excellent electromagnetic properties: Basalt fiber has good electromagnetic shielding properties and is suitable for application scenarios that require electromagnetic shielding.

[0007] 5. Flame retardant properties: Basalt fiber itself has good flame retardant properties, which can improve the flame retardancy of composite materials to a certain extent.

[0008] 6. Sound insulation performance: Basalt fiber composite materials have good sound insulation effect and can be used to make sound insulation walls, sound insulation boards, etc.

[0009] Based on these characteristics and advantages, it becomes an ideal polymer reinforcement material. The composite material formed by adding basalt fiber to the polymer can significantly improve the mechanical properties of the material. Therefore, basalt fiber is widely used in military industry, construction, aerospace and other fields.

[0010] However, despite the many advantages of basalt fiber composites, they also face some challenges in practical applications. In particular, when basalt fibers are added to a polymer matrix to form a composite material, the polymer material contains a large amount of hydrocarbon elements and is flammable. Under high temperature conditions, the polymer melt will infiltrate the surface of the basalt fiber and generate interfacial tension. This phenomenon is called the "wick effect." Specifically, the polymer melt quickly infiltrates, spreads, and flows to the combustion area through the surface of the basalt fiber, further increasing the fire hazard of the polymer composite material, making the polymer composite material with the addition of basalt fibers more difficult to flame retardantly modify, thereby limiting its development and application.

[0011] In order to reduce the flammability of basalt fiber reinforced polymer materials, the current common solution is to compound or add a large amount of flame retardants to polymer / basalt fiber composites to suppress the "wick effect". However, this method has obvious limitations: 1. Degradation of mechanical properties: The addition of a large amount of flame retardants often reduces the mechanical properties of composite materials, which inhibits the gain effect brought by basalt fibers and affects the overall performance of the material. 2. Environmental issues: Some flame retardants may release harmful substances at high temperatures, which will have adverse effects on human health and the environment. 3. Cost issues: The addition of a large amount of flame retardants will increase the cost of the material, affecting its economy and market competitiveness. Therefore, it is of great significance to conduct secondary research and development on basalt fibers so that they can suppress the "wick effect" while ensuring high mechanical properties and flame retardant properties. Summary of the invention

[0012] The present invention is intended to provide a flame retardant modified basalt fiber, a flame retardant modified basalt fiber reinforced PET material and a preparation method thereof, aiming to suppress the "wick effect" while ensuring high mechanical properties and flame retardant properties.

[0013] To achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a flame-retardant modified basalt fiber, after the basalt fiber is modified by amino, a halogen-free flame retardant is grafted on the surface of the basalt fiber to modify the surface of the basalt fiber, and the halogen-free flame retardant is hydroquinone-modified phenylphosphinoyl dichloride.

[0014] Preferably, as an improvement, the amount of the halogen-free flame retardant added is 8-12 wt % of the mass of the amino-modified glass fiber.

[0015] Preferably, as an improvement, the amount of the halogen-free flame retardant added is 8 wt % of the mass of the amino-modified glass fiber.

[0016] Preferably, as an improvement, a method for preparing flame retardant modified basalt fiber comprises the following steps:

[0017] S1, phenylphosphoryl dichloride undergoes substitution reaction to obtain hydroquinone-modified phenylphosphoryl dichloride FR-A;

[0018] S2, amino modification of basalt fiber to obtain BF-NH2;

[0019] S3. Preparation of flame retardant modified basalt fiber BF-NH2-FR: phenylphosphoryl chloride is subjected to substitution reaction to obtain hydroquinone-modified phenylphosphoryl chloride FR-A solution, and then BF-NH2 is added to the FR-A mixed solution, and the reaction is continued to obtain flame retardant modified basalt fiber (BF-NH2-FR).

[0020] Preferably, as an improvement, in step S2, the amino coupling agent is dissolved in an organic solvent, and then the basalt fiber is added, and the reaction is followed by washing and drying to obtain the obtained basalt fiber.

[0021] Preferably, as an improvement, the amino coupling agent is coupling agent KH-550.

[0022] Preferably, as an improvement, a flame retardant modified basalt fiber reinforced PET material includes, by mass, 50-60 parts of PET resin, 15-30 parts of BF-NH2-FR, 2-5 parts of melamine cyanurate, 5-8 parts of hypophosphite, 1-3 parts of toughening agent, 1-3 parts of compatibilizer, 0.1-1 part of nucleating agent, 0.1-1 part of lubricant, 0.1-1 part of antioxidant, and 0.1-2 parts of flame retardant synergist.

[0023] Preferably, as an improvement, the PET resin is at least one of PET-WK801, PET-WP66151, PET-WP66152, and PET-BL02, and the melt index of the PET resin is 0.1 to 100; the melamine cyanurate 1% thermal weight loss is ≥330°C, the hypophosphite is inorganic aluminum hypophosphite; the toughening agent is methyl methacrylate-butadiene-styrene toughening agent M-701, M-722, ethylene methacrylate toughening agent AX89 00, at least one of ethylene-ethyl acrylate toughener 4700; the compatibilizer is at least one of SOG-03, SOG-02, and POE-g-GMA; the nucleating agent is a crystalline nucleating agent; the lubricant is at least one of pentaerythritol stearate, white oil, silicone oil, polyethylene wax, silicone and amide wax; the antioxidant is antioxidant 168, antioxidant 1010 or antioxidant 1098; the flame retardant synergist is at least one of anhydrous zinc borate, zinc sulfide, anhydrous zinc borate, and phosphite.

[0024] Preferably, as an improvement, a flame retardant modified basalt fiber reinforced PET material includes, by mass, 50 to 60 parts of PET-WP66151, 15 to 30 parts of BF-NH2-FR, 2 to 5 parts of melamine cyanurate, 5 to 8 parts of inorganic aluminum hypophosphite, 1 to 3 parts of AX8900, 1 to 3 parts of compatibilizer SOG-03, 0.1 to 2 parts of anhydrous zinc borate, 0.1 to 1 part of nucleating agent P250, 0.1 to 1 part of dispersant pentaerythritol stearate, 0.1 to 1 part of white oil, and 0.1 to 1 part of antioxidant 168.

[0025] Preferably, as an improvement, a method for preparing a flame retardant modified basalt fiber reinforced PET material comprises the following steps:

[0026] Step 1: Add melamine cyanurate, hypophosphite and flame retardant synergist into a high-speed mixer and stir at room temperature for 5 to 30 minutes;

[0027] Step 2: Add PET resin, BF-NH2-FR, toughening agent, compatibilizer, nucleating agent, lubricant and antioxidant to the mixture of step 1, and stir for 5 to 30 minutes;

[0028] The mixture of step 3 and step 2 is extruded through a twin-screw extruder at a temperature of 200-260° C., and then through the processes of drawing and pelletizing, screening and dehydration to obtain flame-retardant reinforced PET granules; the temperatures of each section of the extruder are 220±10, 240±10, 250±10, 250±10, 260±10, 260±10, 250±10, 250±10, 240±10° C., the main screw speed is 120r / min, and the feeding frequency is 10Hz.

[0029] The principle and advantages of this solution are: in actual application, in this technical solution, in view of the technical problems that the "wick effect" and mechanical properties and flame retardant properties of basalt fibers in the prior art cannot be taken into account when used in composite materials, the inventor focuses on exploring the modification of basalt fibers. By grafting halogen-free organic flame retardants on the surface of basalt fibers, the basalt composite materials form a bonding carbon layer on the basalt surface at high temperatures, thereby suppressing the "wick effect". At the same time, the roughness and chemical reaction activity of the surface are increased, the degree of adhesion between the basalt fibers and the matrix is ​​improved, and the flame retardant properties of the system are further enhanced. This technical solution creatively proposes for the first time to apply FR-A to the surface modification of basalt fibers. By designing and optimizing the structure and connection method of FR-A and basalt fibers, the material can be carbonized at a relatively low temperature and cross-linked with polymer materials at high temperatures to form a carbon layer with high thermal stability. In this way, the technical advantages of suppressing the "wick effect" and taking into account mechanical properties and flame retardant properties are achieved. DETAILED DESCRIPTION

[0030] The following is further described in detail through specific implementations, but the implementation of the present invention is not limited thereto. Unless otherwise specified, the technical means used in the following implementations are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents, etc. used can all be obtained from commercial channels.

[0031] The invention discloses a flame retardant modified basalt fiber. After the basalt fiber is modified by amino, a halogen-free flame retardant is grafted on the surface of the basalt fiber to modify the surface of the basalt fiber.

[0032] The halogen-free flame retardant is FR-A (hydroquinone-modified phenyl phosphoryl dichloride), and the added amount of the halogen-free flame retardant is 8-12wt% of the mass of the amino-modified glass fiber.

[0033] A method for preparing flame-retardant modified basalt fiber comprises the following steps:

[0034] S1, phenylphosphoryl dichloride is subjected to substitution reaction to obtain hydroquinone modified phenylphosphoryl dichloride FR-A, the specific steps are: under nitrogen protection, 2g of hydroquinone and 10g of phenylphosphoryl dichloride are added to a three-necked flask containing 100ml of xylene, react for 0.5-6h under ice bath condition, then react for 8h under condensation reflux at 70°C with magnetic stirring, the stirring speed is 850r / min, the product is washed with ice water 3 times, and vacuum dried for 24h to obtain FR-A, the reaction formula is as follows (I):

[0035]

[0036] S2. Amino modification of basalt fiber to obtain BF-NH2, the specific steps are: first prepare 100g of ethanol aqueous solution (500ml, ethanol: water = 450:50), then add coupling agent KH-550 (125ml), and stir evenly to obtain coupling agent solution; add 50g of basalt fiber chopped yarn (BF) to the prepared coupling agent solution, heat and stir at a constant temperature of 60°C for 2-4h, filter, wash and dry at 80°C to obtain BF-NH2, the structural formula of which is as follows:

[0037]

[0038] S3. Preparation of flame retardant modified basalt fiber (BF-NH2-FR), specifically comprising the following steps: under nitrogen protection, add 2 g of hydroquinone and 10 g of phenylphosphoryl dichloride to a three-necked flask containing 100 ml of xylene, react for 0.5-6 h under ice bath conditions to obtain FR-A solution, then add BF-NH2 obtained in S2, condense and reflux at 70°C with magnetic stirring for 4-6 h, and the stirring speed is 850 r / min. After filtering, the product is washed 3 times with ice water, then washed 3 times with ethanol, and dried at 80°C to obtain flame retardant modified basalt fiber (BF-NH2-FR), with a structural formula as shown in formula (III).

[0039]

[0040] A flame retardant modified basalt fiber reinforced PET (ethylene terephthalate) material comprises, by weight, 50-60 parts of PET resin, 15-30 parts of BF-NH2-FR (flame retardant modified basalt fiber), 2-5 parts of melamine cyanurate, 5-8 parts of hypophosphite, 1-3 parts of toughening agent, 1-3 parts of compatibilizer, 0.1-1 part of nucleating agent, 0.1-1 part of lubricant, 0.1-1 part of antioxidant and 0.1-2 parts of flame retardant synergist.

[0041] The PET resin is at least one of PET-WK801, PET-WP66151, PET-WP66152, and PET-BL02, and the melt index of the PET resin is 0.1-100.

[0042] The 1% thermal weight loss of melamine cyanurate (MCA) is ≥330°C, and the hypophosphite is inorganic aluminum hypophosphite (AHP).

[0043] The toughening agent is an ethylene copolymer toughening agent, specifically at least one of methyl methacrylate-butadiene-styrene (MBS) toughening agents M-701 and M-722, ethylene methacrylate (MMA) toughening agent AX8900, and ethylene-ethyl acrylate (EEA) toughening agent 4700.

[0044] The compatibilizer is a graft polymer containing a GMA functional group, specifically at least one of SOG-03, SOG-02, and POE-g-GMA.

[0045] The nucleating agent is a crystal nucleating agent, specifically at least one of P22, P250, and P252.

[0046] The lubricant is at least one of pentaerythritol stearate, white oil, silicone oil, polyethylene wax, silicone and amide wax.

[0047] The antioxidant is antioxidant 168, antioxidant 1010 or antioxidant 1098.

[0048] The flame retardant synergist is at least one of anhydrous zinc borate, zinc sulfide, anhydrous zinc borate and phosphite.

[0049] A method for preparing a flame retardant modified basalt fiber reinforced PET material comprises the following steps:

[0050] Step 1: Add melamine cyanurate, hypophosphite and flame retardant synergist into a high-speed mixer and stir at room temperature for 5 to 30 minutes;

[0051] Step 2: Add PET resin, BF-NH2-FR, toughening agent, compatibilizer, nucleating agent, lubricant and antioxidant to the mixture of step 1, and stir for 5 to 30 minutes;

[0052] The mixture of step 3 and step 2 is extruded through a twin-screw extruder at a temperature of 200-260° C., and then through the processes of drawing and pelletizing, screening and dehydration to obtain flame-retardant reinforced PET granules; the temperatures of each section of the extruder are 220±10, 240±10, 250±10, 250±10, 260±10, 260±10, 250±10, 250±10, 240±10° C., the main screw speed is 120r / min, and the feeding frequency is 10Hz.

[0053] Example 1 (treating glass fiber with halogen-free flame retardant, adding 12%)

[0054] A method for preparing flame-retardant modified basalt fiber comprises the following steps:

[0055] S1. First, FR-A is prepared by stirring and reacting hydroquinone with phenylphosphoryl dichloride.

[0056] S2. Add 5 wt% (5 g) of amino coupling agent KH550 to 100 g of ethanol aqueous solution (500 ml, ethanol: water = 450:50) to prepare a coupling agent solution. After uniform stirring, add basalt fiber chopped yarn, heat and stir at a constant temperature of 60°C for 2-4 hours, filter, wash and dry at 80°C to obtain BF-NH2.

[0057] S3. Under nitrogen protection, add 2 g of hydroquinone and 10 g of phenylphosphoryl dichloride to a three-necked flask filled with 100 ml of xylene, and react for 0.5-6 h in an ice bath to obtain FR-A solution. Then add BF-NH2 obtained in S2, and react under condensation reflux and magnetic stirring at 70°C for 4-6 h. The stirring speed is 850 r / min. After filtering, the product is washed 3 times with ice water, 3 times with ethanol, and dried at 80°C to obtain BF-NH2-FR.

[0058] A flame retardant modified basalt fiber reinforced PET material comprises the following raw material components in parts by weight: 153 parts of PET-WP6615, 30 parts of BF-NH2-FR, 7.2 parts of inorganic aluminum hypophosphite (AHP), 4.8 parts of melamine cyanurate (MCA), 1.5 parts of toughening agent AX8900, 1.5 parts of compatibilizer SOG-03, 0.3 parts of anhydrous zinc borate, 0.5 parts of pentaerythritol stearate (PETS), 0.2 parts of silicone oil, 0.5 parts of nucleating agent P250, and 0.5 parts of antioxidant 168.

[0059] A method for preparing a flame retardant modified basalt fiber reinforced PET material comprises the following steps:

[0060] Step 1: Add melamine cyanurate (MCA), inorganic aluminum hypophosphite (AHP) and anhydrous zinc borate into a high-speed mixer and stir at room temperature for 5 to 30 minutes;

[0061] Step 2: Add PET-WP66151, BF-NH2-FR, AX8900, SOG-03, P250, pentaerythritol stearate (PETS), silicone oil, and antioxidant 168 to the mixture of step 1, and stir for 5 to 30 minutes;

[0062] Step 3, the mixture of step 2 is extruded through a twin-screw extruder at a temperature of 200-260°C, and then through the processes of drawing and pelletizing, screening and dehydration to obtain flame-retardant reinforced PET granules; the temperatures of each section of the extruder are 220±10, 240±10, 250±10, 250±10, 260±10, 260±10, 250±10, 250±10, 240±10°C, the main screw speed is 120r / min, and the feeding frequency is 10Hz.

[0063] Example 2

[0064] The difference between this embodiment and embodiment 1 is that: in this embodiment, when the basalt fiber is modified by a halogen-free flame retardant, the amount of the flame retardant added is 10% (the amount of the flame retardant added in embodiment 1 is 12%). In this embodiment, a flame-retardant modified basalt fiber reinforced PET material comprises the following raw material components in parts by weight: 55 parts of PET-WP66151, 30 parts of BF-NH2-FR, 6 parts of inorganic aluminum hypophosphite (AHP), 4 parts of melamine cyanurate (MCA), 1.5 parts of toughening agent AX8900, 1.5 parts of compatibilizer SOG-03, 0.3 parts of anhydrous zinc borate, 0.5 parts of pentaerythritol stearate (PETS), 0.2 parts of silicone oil, 0.5 parts of nucleating agent P250, and 0.5 parts of antioxidant 168.

[0065] Example 3

[0066] The difference between this embodiment and embodiment 1 is that when the basalt fiber is modified by a halogen-free flame retardant in this embodiment, the amount of the flame retardant added is 8% (the amount of the flame retardant added in embodiment 1 is 12%). In this embodiment, a flame-retardant modified basalt fiber reinforced PET material comprises the following raw material components in parts by weight: 57 parts of PET-WP66151, 30 parts of BF-NH2-FR, 4.8 parts of inorganic aluminum hypophosphite (AHP), 3.2 parts of melamine cyanurate (MCA), 1.5 parts of toughening agent AX8900, 1.5 parts of compatibilizer SOG-03, 0.3 parts of anhydrous zinc borate, 0.5 parts of pentaerythritol stearate (PETS), 0.2 parts of silicone oil, 0.5 parts of nucleating agent P250, and 0.5 parts of antioxidant 168.

[0067] Comparative Example 1

[0068] The difference between this comparative example and Example 1 is that in this comparative example, BF-NH2-FR is replaced by unmodified chopped basalt fibers.

[0069] Comparative Example 2

[0070] The difference between this comparative example and Example 2 is that in this comparative example, BF-NH2-FR is replaced by unmodified chopped basalt fibers.

[0071] Comparative Example 3

[0072] The difference between this comparative example and Example 3 is that in this comparative example, BF-NH2-FR is replaced by unmodified chopped basalt fibers.

[0073] Comparative Example 4

[0074] The formula of the flame retardant modified basalt fiber reinforced PET material in this comparative example is the same as that in Example 1, and the difference from Example 1 is that in this comparative example, BF-NH2 is prepared by only coupling agent treatment, that is, 5wt% (5g) coupling agent KH550 is added to 100g ethanol aqueous solution (500ml, ethanol: water = 450:50) to prepare a coupling agent solution, after uniform stirring, basalt fiber chopped yarn is added, heated and stirred at a constant temperature of 60°C for 2-4h, filtered, washed, and dried at 80°C to obtain BF-NH2.

[0075] Comparative Example 5

[0076] The formula of the flame retardant modified basalt fiber reinforced PET material in this comparative example is the same as that in Example 2, and the difference from Example 2 is that in this comparative example, BF-NH2 is prepared only by coupling agent treatment, that is, 5wt% (5g) coupling agent KH550 is added to 100g ethanol aqueous solution (500ml, ethanol: water = 450:50) to prepare a coupling agent solution, after uniform stirring, basalt fiber chopped yarn is added, heated and stirred at a constant temperature of 60°C for 2-4h, filtered, washed, and dried at 80°C to obtain BF-NH2.

[0077] Comparative Example 6

[0078] The formula of the flame retardant modified basalt fiber reinforced PET material in this comparative example is the same as that in Example 3, and the difference from Example 3 is that in this comparative example, BF-NH2 is prepared only by coupling agent treatment, that is, 5wt% (5g) coupling agent KH550 is added to 100g ethanol aqueous solution (500ml, ethanol: water = 450:50) to prepare a coupling agent solution, after uniform stirring, basalt fiber chopped yarn is added, heated and stirred at a constant temperature of 60°C for 2-4h, filtered, washed, and dried at 80°C to obtain BF-NH2.

[0079] Comparative Example 7

[0080] The formula of the flame-retardant modified basalt fiber reinforced PET material in this comparative example is the same as that in Example 3, the difference from Example 3 is that in this comparative example, unmodified chopped basalt fibers and FR-A are used to replace BF-NH2-FR, wherein the basalt fibers and FR-A are converted in proportion.

[0081] In order to facilitate the comparison of the formulations of the embodiments and comparative examples, the following Table 1 is formed: In Table 1, “ / ” means no addition.

[0082] Table 1: List of Examples and Comparative Examples

[0083]

[0084] Experimental Example 1 Flame retardant and mechanical properties test

[0085] The flame retardant and mechanical properties of the flame retardant reinforced PET materials prepared in the above embodiments and comparative examples are tested, and the specific method is as follows: the composite PET materials prepared in the above embodiments and comparative examples are used as raw materials, the raw materials are dried and mixed evenly by a high mixer, and then melt-extruded and granulated by a screw extruder, and the obtained pellets are dried at 80°C for 12 hours and then injection molded by an injection molding machine to obtain test samples. The temperatures of each section of the extruder are 220±10, 240±10, 250±10, 250±10, 260±10, 260±10, 250±10, 250±10, 240±10°C, the main screw speed is 120r / min, and the feeding frequency is 10Hz.

[0086] The flame retardant performance test method refers to GB / T 2408-2008 and ASTM D2863;

[0087] Mechanical properties test methods refer to GB / T 1040.1-2018 and GB / T 1843-2008.

[0088] The experiment was repeated three times for each group, and the results are shown in Table 2. The results show that the flame retardant and mechanical properties of the flame retardant reinforced PET composite materials obtained in each embodiment of the technical solution are excellent, and the flame retardant properties of the comparative examples using unmodified basalt fibers and basalt fibers treated only with coupling agents are significantly inferior to the test results of the embodiments of the present invention.

[0089] Table 2 Flame retardant properties and mechanical properties test results of each embodiment and comparative example

[0090]

[0091]

[0092] The above is only an embodiment of the present invention, and the common knowledge such as the known specific technical solutions and / or characteristics in the solution is not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical solution of the present invention, several modifications and improvements can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.

Claims

1. A flame retardant modified basalt fiber, characterized in that: After the basalt fiber is modified by amino, a halogen-free flame retardant is grafted onto the surface of the basalt fiber to modify the surface of the basalt fiber. The halogen-free flame retardant is hydroquinone-modified phenylphosphoryl dichloride.

2. The flame retardant modified basalt fiber according to claim 1, characterized in that: The added amount of the halogen-free flame retardant is 8-12 wt % of the mass of the amination-modified glass fiber.

3. The flame retardant modified basalt fiber according to claim 2, characterized in that: The added amount of the halogen-free flame retardant is 8 wt % of the mass of the amination-modified glass fiber.

4. A method for preparing flame-retardant modified basalt fiber according to any one of claims 1 to 3, characterized in that: The steps include: S1, phenylphosphoryl dichloride undergoes substitution reaction to obtain hydroquinone-modified phenylphosphoryl dichloride FR-A; S2, amino modification of basalt fiber to obtain BF-NH2; S3. Preparation of flame retardant modified basalt fiber BF-NH2-FR: phenylphosphoryl dichloride is subjected to substitution reaction to obtain hydroquinone-modified phenylphosphoryl dichloride FR-A solution, and then BF-NH2 is added to the FR-A mixed solution, and the reaction is continued to obtain the flame retardant modified basalt fiber BF-NH2-FR.

5. The method for preparing flame-retardant modified basalt fiber according to claim 4, characterized in that: In step S2, the amino coupling agent is dissolved in an organic solvent, and then the basalt fiber is added, and the reaction is followed by washing and drying.

6. The method for preparing flame-retardant modified basalt fiber according to claim 5, characterized in that: The amino coupling agent is coupling agent KH-550.

7. A flame retardant modified basalt fiber reinforced PET material, characterized in that: Calculated by mass, it includes 50-60 parts of PET resin, 15-30 parts of BF-NH2-FR, 2-5 parts of melamine cyanurate, 5-8 parts of hypophosphite, 1-3 parts of toughening agent, 1-3 parts of compatibilizer, 0.1-1 part of nucleating agent, 0.1-1 part of lubricant, 0.1-1 part of antioxidant and 0.1-2 parts of flame retardant synergist.

8. The flame retardant modified basalt fiber reinforced PET material according to claim 7, characterized in that: The PET resin is at least one of PET-WK801, PET-WP66151, PET-WP66152, and PET-BL02, and the melt index of the PET resin is 0.1 to 100; the melamine cyanurate 1% thermal weight loss is ≥330°C, the hypophosphite is inorganic aluminum hypophosphite; the toughening agent is methyl methacrylate-butadiene-styrene toughening agent M-701, M-722, ethylene methacrylate toughening agent AX8900, ethylene The invention comprises at least one of ethylene-ethyl acrylate toughening agent 4700; the compatibilizer is at least one of SOG-03, SOG-02 and POE-g-GMA; the nucleating agent is a crystallization nucleating agent; the lubricant is at least one of pentaerythritol stearate, white oil, silicone oil, polyethylene wax, silicone and amide wax; the antioxidant is antioxidant 168, antioxidant 1010 or antioxidant 1098; the flame retardant synergist is at least one of anhydrous zinc borate, zinc sulfide, anhydrous zinc borate and phosphite.

9. The flame retardant modified basalt fiber reinforced PET material according to claim 8, characterized in that: Calculated by mass, it includes 50-60 parts of PET-WP66151, 15-30 parts of BF-NH2-FR, 2-5 parts of melamine cyanurate, 5-8 parts of inorganic aluminum hypophosphite, 1-3 parts of AX8900, 1-3 parts of compatibilizer SOG-03, 0.1-2 parts of anhydrous zinc borate, 0.1-1 parts of nucleating agent P250, 0.1-1 parts of dispersant pentaerythritol stearate, 0.1-1 parts of white oil, and 0.1-1 parts of antioxidant 168.

10. The method for preparing a flame retardant modified basalt fiber reinforced PET material according to any one of claims 7 to 9, characterized in that: The steps include: Step 1: Add melamine cyanurate, hypophosphite and flame retardant synergist into a high-speed mixer and stir at room temperature for 5 to 30 minutes; Step 2: Add PET resin, BF-NH2-FR, toughening agent, compatibilizer, nucleating agent, lubricant and antioxidant to the mixture of step 1, and stir for 5 to 30 minutes; The mixture of step 3 and step 2 is extruded through a twin-screw extruder at a temperature of 200-260° C., and then through the processes of drawing and pelletizing, screening and dehydration to obtain flame-retardant reinforced PET granules; the temperatures of each section of the extruder are 220±10, 240±10, 250±10, 250±10, 260±10, 260±10, 250±10, 250±10, 240±10° C., the main screw speed is 120r / min, and the feeding frequency is 10Hz.

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