A ceramifiable burn-through resistant polyamide composite and a method for producing the same

Abstract

The present application relates to a kind of ceramicizable burn-through-resistant polyamide composite and its preparation method, ceramicizable burn-through-resistant polyamide composite includes polyamide resin 100 parts by weight fraction, flame retardant 12-18 parts, chopped glass fiber 15-40 parts, glassy flame retardant powder 7-16 parts and composite ceramization powder 20-60 parts;The components and weight fraction in composite ceramization powder are as follows: calcium silicate 60-100 parts, impregnant 0.5-2 parts, low-melting glass powder 40-100 parts;The melting point of glassy flame retardant powder is 340-360 DEG C, and the melting point of low-melting glass powder is 500-650 DEG C;Method: first, prepare composite ceramization powder according to the proportion, then mix composite ceramization powder and other components into premix according to the proportion, then add into double-screw extruder for granulation, obtain ceramicizable burn-through-resistant polyamide composite.The method is simple, and the polyamide composite prepared has the characteristics of flame retardant, burn-through-resistant, environmental protection and the like.

Description

Technical Field

[0001] This invention belongs to the field of polyamide composite material technology, and relates to a ceramicizable, burn-through resistant polyamide composite material and its preparation method. Background Technology

[0002] Polyamide materials, due to the presence of polar amide groups in their molecular structure, possess characteristics such as high strength, good temperature resistance, excellent chemical resistance, and fatigue resistance, making them commonly used materials in the automotive, electronics, charging equipment, and low-voltage electrical appliance industries. However, with the development of new energy vehicles, especially the increasing demands on battery mileage, battery safety has become a major concern. Therefore, fire-resistant and burn-through-resistant materials offer significant assistance in battery fire prevention and ensuring safe escape time after a battery fire in new energy vehicles. Currently, commonly used fire-resistant and burn-through-resistant materials mainly include metallic aluminum, thermosetting materials, and cross-linked polymers. However, these materials suffer from high density, difficulty in recycling, and limitations in molding, which hinders automotive material recycling and weight reduction to meet battery mileage requirements, thus limiting their use.

[0003] CN112980152A discloses a flame-retardant polyester material with fire resistance and its preparation method. The material comprises the following components in parts by weight: 33-53 parts of thermoplastic polyester or polyamide, 5-20 parts of thermoplastic special engineering plastic resin, 13-20 parts of flame retardant, 1.3-8 parts of flame retardant synergist, 2.0-5 parts of flame retardant synergist, 10-30 parts of filler, 0.1-0.8 parts of antioxidant, and 0.2-1 parts of lubricant. The method for preparing the polyester material is simple and easy to implement. It utilizes the high melting point of polyester / polyamide materials and special engineering plastics, and the characteristic of short-cut glass fibers forming a through-network to support the polymer melt. The supporting material will not collapse and form perforations during combustion. Furthermore, because special engineering plastics have a high charring rate, and the addition of flame retardant synergists can further increase the charring density, when the part made of this material is continuously burned, the material can char in time to maintain the original shape of the part and prevent it from being burned through, thus playing a fire-resistant role.

[0004] However, this existing technology uses glass fiber as a network structure, adds special engineering plastics to increase the charring rate, and compounded flame retardant synergists to further increase the charring rate. It uses surface charring to prevent the material from being burned through, thus playing a fireproof role. However, it cannot significantly improve the burn-through resistance time because the amount of special engineering plastics and flame retardant synergists added is relatively small. The surface charring formed cannot completely prevent the spread of heat. After burning for a certain period of time, the material will burn through and catch fire, which cannot meet the requirements for safe escape. Summary of the Invention

[0005] The purpose of this invention is to solve the above-mentioned problems in the prior art and to provide a ceramicizable burn-through resistant polyamide composite material and its preparation method.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A ceramicizable, heat-resistant polyamide composite material, by weight, comprises 100 parts of polyamide resin, 12-18 parts of flame retardant, 15-40 parts of chopped glass fiber, 7-16 parts of glassy flame retardant powder, and 20-60 parts of composite ceramicizing powder.

[0008] The components and their weight percentages in the composite ceramic powder are as follows: 60-100 parts calcium silicate, 0.5-2 parts wetting agent, and 40-100 parts low melting point glass powder;

[0009] The melting point of glassy flame retardant powder is 340-360℃, while the melting point of low-melting-point glass powder is 500-650℃.

[0010] This invention solves the problems existing in CN112980152A because it utilizes glassy flame-retardant powder to quickly form a film to isolate oxygen during combustion. It combines flame retardant with calcium silicate, which has high heat capacity and low thermal conductivity. This results in calcium silicate absorbing a large amount of heat and having poor thermal conductivity during combustion, leading to a slower heat transfer rate to the interior of the material and reducing the combustion speed. At the same time, it utilizes low-melting-point glass powder to melt upon heating during combustion, bonding calcium silicate and chopped glass fibers to form a ceramic structure, thereby significantly improving the material's burn-through resistance time.

[0011] As a preferred technical solution:

[0012] The ceramicizable, heat-resistant polyamide composite material described above, wherein the polyamide resin is one or more of PA6, PA66, PA56, PA6T / 66, PA66 / PA6, PA612, PA610, and PA6T / 6I / 66.

[0013] The flame retardant of the ceramicizable heat-resistant polyamide composite material described above is aluminum diisobutylphosphite and / or aluminum diethylphosphite.

[0014] The ceramicizable heat-resistant polyamide composite material described above uses chopped glass fibers with a chopped length of 3-4.5 mm and a single filament diameter of 7-11 μm.

[0015] As described above, the glassy flame-retardant powder of the ceramicizable heat-resistant polyamide composite material has a protection temperature range of 350-600℃. The protection temperature range provides the best protection for the material. Below the protection temperature range, the material does not melt, while above the protection temperature range, it will burn and fail.

[0016] As described above, the ceramizable, heat-resistant polyamide composite material contains calcium silicate with a particle size of 12-18 μm, a silica content of 40-52 wt%, and a calcium oxide content of 42-48 wt%. Particle size is crucial for the dispersion of calcium silicate in the resin; too fine a particle size results in poor dispersion, while too coarse a particle size leads to unsatisfactory effects. Silica plays a stabilizing and reinforcing role in calcium silicate, being one of its main components. It provides silicon atoms to silicate ions, which then form silicon-oxygen bonds with other silicate ions, creating a three-dimensional network structure. This structural stability gives calcium silicate a high melting point and fire resistance, and also hinders heat and flame conduction. Calcium oxide primarily functions as a colorant and reaction regulator in calcium silicate. The reaction of calcium oxide with silicate to form silicates regulates the acid-base properties of calcium silicate. Since alkalinity affects the flame-retardant effect of hypophosphite, this ratio of calcium silicate yields the best results.

[0017] The ceramicizable, heat-resistant polyamide composite material described above uses polydimethylsiloxane as the impregnating agent.

[0018] As described above, in a ceramicizable heat-resistant polyamide composite material, the content of sodium oxide in the low-melting-point glass powder is 2-8 wt%, and the content of potassium oxide is 1-4 wt%. The content of sodium oxide and potassium oxide affects the melting point of the low-melting-point glass powder.

[0019] The ceramicizable, heat-resistant polyamide composite material described above further includes, by weight, 0.3-0.6 parts of antioxidant and 0.2-0.6 parts of dispersant.

[0020] As described above, in a ceramicizable, heat-resistant polyamide composite material, the antioxidant is composed of a primary antioxidant and an auxiliary antioxidant in a mass ratio of 1:1.

[0021] The main antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098). One or more of them;

[0022] The auxiliary antioxidant is bis(2,4-dicumylphenyl)pentaerythritol diphosphite (S9228). and One or more of them;

[0023] The dispersant is one or more of silicone powder and TAF.

[0024] As described in any of the preceding items, the ceramizable heat-penetration resistant polyamide composite material has a heat-penetration resistance time of 620-730s and a flame retardancy rating of V0 for 0.8mm.

[0025] The present invention also provides a method for preparing a ceramizable, burn-through resistant polyamide composite material as described in any of the preceding claims, comprising the following steps:

[0026] (1) Mix the components in the composite ceramic powder according to the proportion to obtain the composite ceramic powder;

[0027] (2) The composite ceramic powder is mixed with other components according to the ratio to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramic-resistant, heat-resistant polyamide composite material.

[0028] This invention first prepares composite ceramic powder, and then mixes it with other components. Since both calcium silicate and low-melting-point glass powder contain silicon dioxide, wetting with an impregnating agent can effectively disperse the powder and prevent bridging during feeding. At the same time, it can also improve the bonding between calcium silicate and low-melting-point glass powder, thus achieving better results. If all components are mixed together directly, the effect will be reduced.

[0029] As a preferred technical solution:

[0030] As described above, in step (1), the mixing temperature is 40-60℃ and the time is 5-7 min; in step (2), the mixing is carried out in a high-speed mixer with a rotation speed of 220-480 rpm.

[0031] The principle of this invention is as follows:

[0032] This invention can significantly improve the burn-through resistance of polyamides, with the material's burn-through time reaching 620-730 seconds. The reasons are as follows:

[0033] ① This invention utilizes glassy flame retardant powder with a melting point of 350℃ to quickly form a film to isolate oxygen when exposed to flame combustion, thereby hindering the combustion reaction. Flame retardants such as aluminum diisobutylphosphite and aluminum diethylphosphite quickly form carbon during combustion, hindering the transfer of oxygen and heat, and preventing the surface flame from spreading further.

[0034] ② The calcium silicate added in this invention has high heat capacity and low thermal conductivity, which makes calcium silicate absorb a large amount of heat when the material is burned and has poor thermal conductivity, resulting in a slow heat transfer rate to the interior of the material and reducing the combustion rate.

[0035] ③ The composite material of the present invention contains calcium silicate, chopped glass fiber and low melting point glass powder. When the temperature of the polyamide substrate reaches 500-650°C during flame combustion, the low melting point glass powder melts and bonds the calcium silicate and chopped glass fiber, achieving a ceramic-like effect. The ceramic material is similar to the inorganic material formed in a molten state inside the plastic, which reduces the spread of heat and flame, isolates oxygen, and further improves the burn-through resistance of the material.

[0036] Beneficial effects:

[0037] (1) The ceramicizable burn-through resistant polyamide composite material of the present invention has a burn-through time of up to 620-730s, which greatly improves the safe escape time.

[0038] (2) The ceramicizable heat-resistant polyamide composite material of the present invention has a lower density than thermosetting materials and metals, and has good design and molding properties and is environmentally friendly, and can be widely promoted and applied. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0040] The following are the performance testing methods described in the examples:

[0041] Melting point: determined using a DSC analyzer.

[0042] Protection temperature range: determined using a TGA tester.

[0043] Burn-through time: After preparing a sample with a thickness of 3 mm, a spray gun with a flame temperature of 1500℃ was directly applied to the sample to burn through it, and the burn-through time was calculated.

[0044] Flame retardancy rating of 0.8mm: After preparing a sample with a thickness of 0.8mm, test according to UL-94.

[0045] 1.6mm flame retardancy rating: After preparing a sample with a thickness of 1.6mm, test according to UL-94.

[0046] 3.2mm flame retardancy rating: After preparing a sample with a thickness of 3.2mm, test according to UL-94.

[0047] Example 1

[0048] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0049] (1) Preparation of raw materials;

[0050] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 12μm, a silica content of 40wt%, and a calcium oxide content of 48wt%.

[0051] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0052] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-500, sodium alkali metal oxide content is 8wt%, potassium oxide content is 4wt%, melting point is 500℃;

[0053] Polyamide resin: PA6, manufactured by Jiangsu Ruimeifu Industrial Co., Ltd., grade MF800;

[0054] Flame retardant: aluminum diisobutylphosphite;

[0055] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 3mm, and single filament diameter is 7μm;

[0056] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0057] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a mass ratio of 1:1. The primary antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098), and the secondary antioxidant is bis(2,4-dicumylphenyl)pentaerythritol diphosphite (S9228).

[0058] Dispersant: Silicone powder;

[0059] (2) By weight, 60 parts of calcium silicate, 0.5 parts of wetting agent and 40 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 40℃ and the time is 5min;

[0060] (3) By weight, 100 parts of polyamide resin, 12 parts of flame retardant, 15 parts of chopped glass fiber, 7 parts of glassy flame retardant powder, 20 parts of composite ceramic powder, 0.3 parts of antioxidant and 0.2 parts of dispersant are added to a high-speed mixer with a rotation speed of 220 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0061] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 622s and a flame retardancy rating of V0 at 0.8mm.

[0062] Comparative Example 1

[0063] A method for preparing a polyamide composite material is basically the same as in Example 1, except that: glassy flame retardant powder is not prepared in step (1), and glassy flame retardant powder is not added in step (3).

[0064] The final polyamide composite material had a burn-through time of 410s and a flame retardancy rating of V0 at 3.2mm.

[0065] Comparing Comparative Example 1 and Example 1, it can be seen that the burn-through resistance and flame retardant properties of the ceramicizable burn-through resistant polyamide composite material of Example 1 are significantly stronger than those of the polyamide composite material of Comparative Example 1. This is because glassy flame retardant powder was added in Example 1, which can quickly form a film to isolate oxygen when the composite material is subjected to flame combustion, hindering heat conduction and preventing the combustion reaction from proceeding. This improves the burn-through resistance of the material while also improving its flame retardant properties.

[0066] Comparative Example 2

[0067] A method for preparing a polyamide composite material is basically the same as in Example 1, except that calcium silicate is not prepared in step (1) and calcium silicate is not added in step (2).

[0068] The final polyamide composite material had a burn-through time of 508s and a flame retardancy rating of V0 at 1.6mm.

[0069] Comparing Comparative Example 2 and Example 1, it can be seen that the burn-through resistance and flame retardant properties of the ceramicizable burn-through resistant polyamide composite material of Example 1 are significantly stronger than those of the polyamide composite material of Comparative Example 2. This is because the calcium silicate added in Example 1 has the characteristics of high heat capacity and low thermal conductivity. When the composite material is burning, it can absorb a large amount of heat and reduce the energy of heat conduction of the polyamide resin. The heat generated by the flame is transferred to the interior of the composite material at a slower rate, thereby achieving the effects of burn-through resistance and flame retardancy.

[0070] Comparative Example 3

[0071] A method for preparing a polyamide composite material is basically the same as in Example 1, except that: low melting point glass powder is not prepared in step (1) and low melting point glass powder is not added in step (2).

[0072] The final polyamide composite material had a burn-through time of 364s and a flame retardancy rating of V0 at 1.6mm.

[0073] Comparing Comparative Example 3 and Example 1, it can be seen that the burn-through resistance and flame retardant properties of the ceramicizable burn-through resistant polyamide composite material of Example 1 are significantly stronger than those of the polyamide composite material of Comparative Example 3. This is because the low-melting-point glass powder added in Example 1 can begin to melt when the temperature of the polyamide substrate reaches above its melting point during flame combustion, thus bonding the inorganic calcium silicate and chopped glass fibers to achieve a ceramicizable effect. The ceramicized material is similar to the inorganic material that forms a molten state inside the plastic, reducing the spread of heat and flame, isolating oxygen, and further improving the burn-through resistance and flame retardant properties of the material.

[0074] Comparative Example 4

[0075] A method for preparing a polyamide composite material is basically the same as in Example 1, except that: no chopped glass fibers are prepared in step (1) and no chopped glass fibers are added in step (3).

[0076] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 427s and a flame retardancy rating of V0 at 0.8mm.

[0077] Comparing Comparative Example 4 and Example 1, it can be seen that the burn-through resistance and flame retardant properties of the ceramicizable burn-through resistant polyamide composite material of Example 1 are significantly stronger than those of the polyamide composite material of Comparative Example 4. This is because the chopped glass fiber added in Example 1 is a reinforcing agent, which can greatly improve the mechanical properties of the material, including tensile strength, flexural strength, flexural modulus and impact strength. It can also greatly improve the heat resistance of the material. When the material is heated during combustion, the chopped glass fiber can provide sufficient skeleton support and bonding strength for the molten low-melting-point glass powder, thus delaying the time when the material is burned through.

[0078] Comparative Example 5

[0079] A method for preparing a polyamide composite material is basically the same as in Example 1, except that: no flame retardant is prepared in step (1) and no flame retardant is added in step (3).

[0080] The resulting ceramicizable burn-through resistant polyamide composite material has a burn-through time of 254s and a flame retardancy rating of V1 at 3.2mm.

[0081] Comparing Comparative Example 5 and Example 1, it can be seen that the burn-through resistance and flame retardant properties of the ceramicizable burn-through resistant polyamide composite material of Example 1 are significantly stronger than those of the polyamide composite material of Comparative Example 5. This is because the flame retardant added in Example 1 can form a condensed phase during the combustion process of the material, which can isolate the entry of oxygen, prevent the spread of flame, and hinder the combustion reaction. However, no flame retardant was used in Comparative Example 5. Although the addition of low melting point glass powder, glassy flame retardant powder, and calcium silicate can slow down the spread of heat, it cannot prevent the spread of flame in the early stage of combustion, thus affecting the burn-through resistance and flame retardant properties of the material.

[0082] Example 2

[0083] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0084] (1) Preparation of raw materials;

[0085] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 18μm, a silica content of 40wt%, and a calcium oxide content of 48wt%.

[0086] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0087] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-550, sodium alkali metal oxide content is 6wt%, potassium oxide content is 4wt%, melting point is 550℃;

[0088] Polyamide resin: PA66, manufactured by Pingdingshan Shenma Engineering Plastics Co., Ltd., grade FYR2.7;

[0089] Flame retardant: aluminum diethylphosphinate;

[0090] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 3mm, and single filament diameter is 11μm;

[0091] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0092] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, the primary antioxidant being... Co-antioxidant

[0093] Dispersant: Silicone powder;

[0094] (2) By weight, 100 parts of calcium silicate, 2 parts of wetting agent and 100 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 40℃ and the time is 7min;

[0095] (3) By weight, 100 parts of polyamide resin, 18 parts of flame retardant, 40 parts of chopped glass fiber, 16 parts of glassy flame retardant powder, 20 parts of composite ceramic powder, 0.6 parts of antioxidant and 0.6 parts of dispersant are added to a high-speed mixer with a rotation speed of 260 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0096] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 712s and a flame retardancy rating of V0 at 0.8mm.

[0097] Example 3

[0098] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0099] (1) Preparation of raw materials;

[0100] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 12μm, a silica content of 52wt%, and a calcium oxide content of 42wt%.

[0101] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0102] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-550, sodium alkali metal oxide content is 6wt%, potassium oxide content is 4wt%, melting point is 550℃;

[0103] Polyamide resin: PA56, manufactured by Shanghai Kaisai Biotechnology Co., Ltd., brand name ECOPENT1273;

[0104] Flame retardant: aluminum diethylphosphinate;

[0105] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 4.5mm, and monofilament diameter is 11μm;

[0106] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0107] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, the primary antioxidant being... Co-antioxidant

[0108] Dispersant: Silicone powder;

[0109] (2) By weight, 60 parts of calcium silicate, 1.2 parts of wetting agent and 100 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 60℃ and the time is 7min;

[0110] (3) By weight, 100 parts of polyamide resin, 18 parts of flame retardant, 15 parts of chopped glass fiber, 7 parts of glassy flame retardant powder, 50 parts of composite ceramic powder, 0.6 parts of antioxidant and 0.6 parts of dispersant are added to a high-speed mixer with a rotation speed of 360 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0111] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 725s and a flame retardancy rating of V0 at 0.8mm.

[0112] Example 4

[0113] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0114] (1) Preparation of raw materials;

[0115] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 18μm, a silica content of 52wt%, and a calcium oxide content of 42wt%.

[0116] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0117] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-550, sodium alkali metal oxide content is 6wt%, potassium oxide content is 4wt%, melting point is 550℃;

[0118] Polyamide resin: PA6T / 66, manufactured by Celanese, USA, grade HTN510EFT NC010;

[0119] Flame retardant: aluminum diethylphosphinate;

[0120] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 3mm, and single filament diameter is 10μm;

[0121] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0122] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio. The primary antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098), and the secondary antioxidant is...

[0123] Dispersant: TAF;

[0124] (2) By weight, 100 parts of calcium silicate, 1.8 parts of wetting agent and 40 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 60℃ and the time is 6min;

[0125] (3) By weight, 100 parts of polyamide resin, 12 parts of flame retardant, 40 parts of chopped glass fiber, 16 parts of glassy flame retardant powder, 25 parts of composite ceramic powder, 0.3 parts of antioxidant and 0.2 parts of dispersant are added to a high-speed mixer with a rotation speed of 400 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0126] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 643s and a flame retardancy rating of V0 at 0.8mm.

[0127] Example 5

[0128] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0129] (1) Preparation of raw materials;

[0130] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 13μm, a silica content of 45wt%, and a calcium oxide content of 46wt%.

[0131] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0132] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-600, sodium alkali metal oxide content is 2wt%, potassium oxide content is 1wt%, melting point is 650℃;

[0133] Polyamide resin: PA66 / 6, manufactured by Solutia Inc., USA, grade 75HF;

[0134] Flame retardant: aluminum diisobutylphosphite;

[0135] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 4.5mm, and monofilament diameter is 7μm;

[0136] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0137] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, the primary antioxidant being... Co-antioxidant

[0138] Dispersant: TAF;

[0139] (2) By weight, 75 parts of calcium silicate, 0.7 parts of wetting agent and 68 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 55℃ and the time is 6.5min;

[0140] (3) By weight, 100 parts of polyamide resin, 14 parts of flame retardant, 20 parts of chopped glass fiber, 14 parts of glassy flame retardant powder, 40 parts of composite ceramic powder, 0.4 parts of antioxidant and 0.3 parts of dispersant are added to a high-speed mixer with a rotation speed of 480 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0141] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 682s and a flame retardancy rating of V0 at 0.8mm.

[0142] Example 6

[0143] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0144] (1) Preparation of raw materials;

[0145] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 15μm, a silica content of 50wt%, and a calcium oxide content of 49wt%.

[0146] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0147] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-650, sodium alkali metal oxide content is 2wt%, potassium oxide content is 1wt%, melting point is 650℃;

[0148] Polyamide resin: PA612, manufactured by Celanese, USA, grade 151L NC010;

[0149] Flame retardant: aluminum diisobutylphosphite;

[0150] Chopped fiberglass: Manufacturer is Chongqing International Composite Materials Co., Ltd., grade is ECS301HP-3-H, chopped length is 4.5mm, and monofilament diameter is 11μm;

[0151] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0152] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, the primary antioxidant being... Co-antioxidant

[0153] Dispersant: A mixture of silicone powder and TAF in a mass ratio of 1:1;

[0154] (2) By weight, 80 parts of calcium silicate, 0.9 parts of wetting agent and 49 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 50℃ and the time is 5min;

[0155] (3) By weight, 100 parts of polyamide resin, 13 parts of flame retardant, 30 parts of chopped glass fiber, 15 parts of glassy flame retardant powder, 30 parts of composite ceramic powder, 0.5 parts of antioxidant and 0.4 parts of dispersant are added to a high-speed mixer with a rotation speed of 420 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0156] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 694s and a flame retardancy rating of V0 at 0.8mm.

[0157] Example 7

[0158] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0159] (1) Preparation of raw materials;

[0160] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 14μm, a silica content of 42wt%, and a calcium oxide content of 47wt%.

[0161] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0162] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-650, sodium alkali metal oxide content is 2wt%, potassium oxide content is 1wt%, melting point is 650℃;

[0163] Polyamide resin: PA610, manufacturer: Evonik, grade: A6161;

[0164] Flame retardant: aluminum diisobutylphosphite;

[0165] Chopped fiberglass: Manufacturer is China Jushi Co., Ltd., grade is 560A, chopped length is 3mm, and monofilament diameter is 10μm;

[0166] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0167] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, the primary antioxidant being... The auxiliary antioxidant is in a 1:1 mass ratio. A mixture;

[0168] Dispersant: TAF;

[0169] (2) By weight, 90 parts of calcium silicate, 1.8 parts of wetting agent and 55 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 45℃ and the time is 5.5min;

[0170] (3) By weight, 100 parts of polyamide resin, 15 parts of flame retardant, 35 parts of chopped glass fiber, 13 parts of glassy flame retardant powder, 25 parts of composite ceramic powder, 0.4 parts of antioxidant and 0.5 parts of dispersant are added to a high-speed mixer with a rotation speed of 240 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0171] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 707s and a flame retardancy rating of V0 at 0.8mm.

[0172] Example 8

[0173] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0174] (1) Preparation of raw materials;

[0175] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 17μm, a silica content of 49wt%, and a calcium oxide content of 45wt%.

[0176] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0177] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-650, sodium alkali metal oxide content is 2wt%, potassium oxide content is 1wt%, melting point is 650℃;

[0178] Polyamide resin: PA6T / 6I / 66, manufactured by Qingdao Sanlibenuo New Material Co., Ltd., grade 1345;

[0179] Flame retardant: aluminum diisobutylphosphite;

[0180] Chopped fiberglass: Manufacturer is China Jushi Co., Ltd., grade is 568A, chopped length is 3mm, and monofilament diameter is 10μm;

[0181] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0182] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, with the primary antioxidant having a 1:1 mass ratio. The mixture, with the auxiliary antioxidant being pentaerythritol diphosphite (S9228) in a mass ratio of 1:1 and bis(2,4-dicumylphenyl)phosphite in an auxiliary antioxidant ratio of 1:1. A mixture;

[0183] Dispersant: TAF;

[0184] (2) By weight, 98 parts of calcium silicate, 1.1 parts of wetting agent and 82 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 45℃ and the time is 7min;

[0185] (3) By weight, 100 parts of polyamide resin, 16 parts of flame retardant, 25 parts of chopped glass fiber, 10 parts of glassy flame retardant powder, 35 parts of composite ceramic powder, 0.6 parts of antioxidant and 0.3 parts of dispersant are added to a high-speed mixer with a rotation speed of 300 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0186] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 687s and a flame retardancy rating of V0 at 0.8mm.

[0187] Example 9

[0188] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0189] (1) Preparation of raw materials;

[0190] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 16μm, a silica content of 51wt%, and a calcium oxide content of 44wt%.

[0191] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0192] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-600, sodium alkali metal oxide content is 2wt%, potassium oxide content is 1wt%, melting point is 650℃;

[0193] Polyamide resin: PA6T / 6, manufactured by Qingdao Sanlibenuo New Material Co., Ltd., grade 1132;

[0194] Flame retardant: a mixture of aluminum diisobutylphosphite and aluminum diethylphosphite in a mass ratio of 1:1;

[0195] Chopped fiberglass: Manufacturer is China Jushi Co., Ltd., grade is 560HD, chopped length is 3mm, and monofilament diameter is 10μm;

[0196] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0197] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio, with the primary antioxidant having a 1:1 mass ratio. A mixture of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098), with an auxiliary antioxidant in a mass ratio of 1:1. A mixture of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (S9228);

[0198] Dispersant: TAF;

[0199] (2) By weight, 83 parts of calcium silicate, 0.6 parts of wetting agent and 77 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 60℃ and the time is 6min;

[0200] (3) By weight, 100 parts of polyamide resin, 17 parts of flame retardant, 15 parts of chopped glass fiber, 9 parts of glassy flame retardant powder, 60 parts of composite ceramic powder, 0.5 parts of antioxidant and 0.2 parts of dispersant are added to a high-speed mixer with a rotation speed of 460 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0201] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 721s and a flame retardancy rating of V0 at 0.8mm.

[0202] Example 10

[0203] A method for preparing a ceramizable, heat-penetration-resistant polyamide composite material, comprising the following specific steps:

[0204] (1) Preparation of raw materials;

[0205] Calcium silicate: Manufacturer is Jiangxi Dishi Mineral Fiber Technology Co., Ltd., with an average particle size of 18μm, a silica content of 42wt%, and a calcium oxide content of 40wt%.

[0206] Sizing agent: polydimethylsiloxane, brand name Dow Corning, grade PMX-200 350cS;

[0207] Low melting point glass powder: Manufacturer is Lianyungang Wohua New Material Technology Co., Ltd., grade is WH-GP-550, sodium alkali metal oxide content is 6wt%, potassium oxide content is 4wt%, melting point is 550℃;

[0208] Polyamide resin: a mixture of PA6 (manufacturer: Jiangsu Ruimeifu Industrial Co., Ltd., grade: MF800) and PA66 (manufacturer: Pingdingshan Shenma Engineering Plastics Co., Ltd., grade: FYR2.7) in a mass ratio of 1:1;

[0209] Flame retardant: a mixture of aluminum diisobutylphosphite and aluminum diethylphosphite in a mass ratio of 2:1;

[0210] Chopped fiberglass: Manufacturer is China Jushi Co., Ltd., grade is 560A, chopped length is 3mm, and monofilament diameter is 10μm;

[0211] Vitreous flame retardant powder: Manufacturer is Anmi Micro-Nano New Materials (Guangzhou) Co., Ltd., grade is FR0135, melting point is 350℃, and protection temperature range is 350-600℃;

[0212] Antioxidant: Composed of a primary antioxidant and a secondary antioxidant in a 1:1 mass ratio. The primary antioxidant is N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (1098) and [other antioxidants] in a 1:1 mass ratio. A mixture, with auxiliary antioxidants as

[0213] Dispersant: TAF;

[0214] (2) By weight, 65 parts of calcium silicate, 1.5 parts of wetting agent and 94 parts of low melting point glass powder are mixed to obtain composite ceramic powder; wherein, the mixing temperature is 50℃ and the time is 5min;

[0215] (3) By weight, 100 parts of polyamide resin, 18 parts of flame retardant, 30 parts of chopped glass fiber, 16 parts of glassy flame retardant powder, 60 parts of composite ceramic powder, 0.3 parts of antioxidant and 0.6 parts of dispersant are added to a high-speed mixer with a rotation speed of 480 rpm to form a premix. The premix is ​​then fed into a twin-screw extruder from the main feed port for granulation to obtain a ceramicizable heat-resistant polyamide composite material.

[0216] The final ceramicizable burn-through resistant polyamide composite material has a burn-through time of 730s and a flame retardancy rating of V0 at 0.8mm.

Claims

1. A ceramifiable burn-through resistant polyamide composite, characterized in that, The polyamide resin is 100 parts, the flame retardant is 12-18 parts, the chopped glass fiber is 15-40 parts, the glassy flame retardant powder is 7-16 parts, the composite ceramifiable powder is 20-60 parts, the antioxidant is 0.3-0.6 parts, and the dispersant is 0.2-0.6 parts by weight; The components and weight parts of the composite ceramifiable powder are as follows: calcium silicate 60-100 parts, wetting agent 0.5-2 parts, and low-melting-point glass powder 40-100 parts; The manufacturer of the glassy flame retardant powder is Anmimicro-nano New Material (Guangzhou) Co., Ltd., the brand is FR0135, and the melting point is 350℃. The melting point of the low-melting-point glass powder is 550-650℃.

2. A ceramifiable burn-through resistant polyamide composite material according to claim 1, characterized in that, The polyamide resin is one or more of PA6, PA66, PA56, PA6T / 66, PA66 / PA6, PA612, PA610, and PA6T / 6I / 66.

3. The ceramifiable burn-through resistant polyamide composite of claim 1, wherein, The flame retardant is aluminum diisobutyl phosphinate and / or aluminum diethyl phosphinate.

4. The ceramifiable burn-through resistant polyamide composite of claim 1, wherein, The chopped glass fiber is a chopped yarn with a chopped length of 3-4.5 mm and a single filament diameter of 7-11 μm.

5. The ceramifiable burn-through resistant polyamide composite of claim 1, wherein, The protection temperature range of the glassy flame retardant powder is 350-600℃.

6. The ceramifiable burn-through resistant polyamide composite of claim 1, wherein, The particle size of the calcium silicate is 12-18 μm, the silicon dioxide content is 40-52 wt%, and the calcium oxide content is 42-48 wt%.

7. The ceramifiable burn-through resistant polyamide composite of claim 1, wherein, The content of alkali metal sodium oxide in the low-melting-point glass powder is 2-8 wt%, and the content of potassium oxide is 1-4 wt%.

8. The ceramifiable burn-through resistant polyamide composite according to any one of claims 1 to 7, characterized in that The burn-through resistant time of the ceramifiable burn-through resistant polyamide composite material is 620-730 s, and the 0.8 mm flame retardant grade is V0.

9. A method of making a burn-through resistant, ceramicizable polyamide composite material as claimed in any one of claims 1 to 8, characterized in that, The method comprises the following steps: (1) mixing the components in the composite ceramifiable powder according to the proportion to obtain the composite ceramifiable powder; (2) mixing the composite ceramifiable powder and other components according to the proportion to form a premix, and then adding the premix into a double-screw extruder for granulation to obtain the ceramifiable burn-through resistant polyamide composite material.