Covalent organic framework material cofs flame-retardant polyamide resin sheet

Abstract

The present application relates to a kind of covalent organic framework material COFs flame-retardant polyamide resin sheet, belong to flame-retardant technical field.The flame-retardant polyamide resin sheet includes the following component and mass percentage content: including the following component and mass percentage content: polyamide 60%~98%, MTM 2%~15%, antioxidant 1010 0.1%~1%And antioxidant 168 0.1%~1%;Flame-retardant polyamide resin sheet is triazine-based COFs material (MTM) High-efficiency flame-retardant effect, improve the char-forming of polyamide resin, reduce the heat release rate of matrix, smoke release amount, strive for more fire evacuation time;The flame-retardant polyamide resin provided by the present application has the advantages of less addition amount, simple preparation method, excellent mechanical property, efficient carbonization flame-retardant performance, low heat release rate and low smoke yield.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of covalent organic framework material (COFs) flame-retardant polyamide resin sheet, belong to flame-retardant technical field. BACKGROUND

[0002] Polyamide (Polyamide, PA for short, nylon) is the general term of polymer with amide group (-CONH-) in macromolecular chain, and it is the most widely used material among the five engineering plastics.PA6 material is the most widely used variety in polyamide, due to its excellent toughness, self-lubricating, heat resistance, oil resistance and other excellent performance, it has extremely wide application in electronic packaging, electrical appliances, transportation and many other fields.

[0003] As an aliphatic material, PA6 contains a large number of methylene structures, which is easy to burn, and the fields including electronic appliances, aerospace, railway transportation require PA6 material to have excellent flame retardant performance and physical and mechanical properties, so it has become the focus of current research to endow PA6 material with excellent flame retardant performance, and the development of efficient halogen-free flame retardant system suitable for polyamide material is particularly important for the environmental protection development of many industries.

[0004] At present, the flame retardant for polyamide mainly includes the following types: (1) halogen-based flame retardant, this kind of flame retardant is initially widely used due to its excellent flame retardant effect, processing convenience and good compatibility with base material. However, in view of the series of environmental protection regulations implemented by the international community in recent years, its use is limited; (2) nitrogen-based flame retardant, mainly taking melamine and its derivatives as the core, the representative products are MCA and MPP, this kind of flame retardant has certain efficiency, but due to the large amount of addition and the easy phase separation with polyamide resin, it is difficult to mix uniformly, which further seriously reduces the mechanical properties of the material; (3) inorganic flame retardant, represented by magnesium hydroxide and aluminum hydroxide, although this kind of flame retardant is environmentally friendly and low in cost, but due to its low flame retardant efficiency, large amount of addition and poor compatibility with polyamide matrix, it leads to significant decrease of mechanical properties, which limits its application in high performance polyamide material; (4) phosphorus-based flame retardant, mainly taking organic phosphinic acid salt as the main component, this kind of flame retardant can inhibit the spread and development of flame by releasing inert free radicals in the heating process. However, in actual fire scene, due to the effect of continuous high temperature, its gas phase flame retardant effect may rapidly decrease, and the control effect of heat release rate and total heat release amount is not ideal, and even due to the presence of phosphorus element, it may increase the smoke production during combustion, which has negative impact on the escape of personnel in fire scene. SUMMARY

[0005] The application aims to provide a covalent organic framework material COFs flame-retardant polyamide resin sheet, which is subjected to high-efficiency flame-retardant effect of triazine-based COFs material (MTM), improves the char-forming property of the polyamide resin, reduces the heat release rate and smoke release amount of the substrate, and strives for more fire evacuation time.

[0006] The application aims to achieve the above-mentioned purpose through the following technical solutions.

[0007] The covalent organic framework material COFs flame-retardant polyamide resin sheet comprises the following components and mass percentages: polyamide 60%-98%, MTM 2%-15%, antioxidant 1010 0.1%-1%, and antioxidant 168 0.1%-1%.

[0008] The component further comprises other additives, and the addition amount of the other additives is not more than 0.5% of the total mass of the component.

[0009] The other additives comprise at least one of an anti-dripping agent, a heat stabilizer, a plasticizer, and a crosslinking agent.

[0010] The flame-retardant polyamide resin sheet is subjected to high-efficiency flame-retardant effect of the material MTM, improves the char-forming property of the polyamide resin sheet, and reduces the heat release rate and smoke release amount of the substrate.

[0011] The MTM is shown in formula A.

[0012]

[0013] The polyamide is selected from one or a mixture of several of PA6, PA66, PA11, PA1212, PA46, PA610, PA612, and PA1010.

[0014] The polyamide is preferably one or a mixture of two of PA6 and PA66.

[0015] The application relates to a preparation method of a polyamide resin sheet with flame-retardant performance.

[0016] The method for preparing the flame-retardant polyamide resin sheet of the covalent organic framework material COFs comprises the following steps: uniformly mixing raw materials, and adding the raw materials into a blending device for melt blending; under the melting condition of the polyamide, extruding by using a screw extruder, and then cutting and collecting particles, and adding the particles into an injection molding machine for injection molding under the melting condition of the polyamide.

[0017] The method for preparing the flame-retardant polyamide resin sheet of the covalent organic framework material COFs comprises the following steps: heating the polyamide to a melting state in a banbury mixer or an open mill, then gradually adding other necessary materials, uniformly mixing the materials, crushing and granulating the materials to obtain the required flame-retardant polyamide resin particles, collecting the particles, and adding the particles into an injection molding machine for injection molding under the melting condition of the polyamide.

[0018] The flame-retardant polyamide resin prepared by the method has good flame-retardant performance, and maintains the original mechanical strength and thermal stability of the polyamide, and is suitable for various industrial application fields, such as electronic appliances, automobile manufacturing, building materials, etc., and meets the market demand for high-performance flame-retardant materials.

[0019] Advantages

[0020] 1. The covalent organic framework material (COFs) flame-retardant polyamide resin sheet has the advantages that, compared with the prior art, the covalent organic framework material is innovatively used in the polyamide resin, and through the synergistic effect of catalytic degradation, heat absorption, interruption of heat exchange by melting drops, dilution of inert gas and condensation phase crosslinking reaction, the polyamide resin is endowed with excellent flame-retardant performance. Firstly, the MTM catalyzes the polyamide resin to degrade in advance, so that the sample quickly forms "low-temperature" melting drops, and a large amount of heat is taken away, so as to interrupt the heat exchange mechanism; secondly, the MTM can change the cracking site of the polyamide molecular chain, so that the process of mainly producing flammable gas during the degradation of the polyamide resin is changed into the crosslinking of part of the polyamide molecules and the carbonization effect; finally, the MTM produces a large amount of inert gas during the degradation, which dilutes the concentration of the flammable gas, and changes the degradation process of the polyamide from the surface to the inside to the simultaneous degradation of the surface and the inside, which is helpful to the rapid crosslinking and carbonization of the inside of the substrate, and the generation of bubbles of aggregated inert gas. Due to the high-efficiency flame-retardant effect of the MTM on the polyamide resin, the peak value of the heat release rate and the smoke production are obviously reduced, and the system is obviously improved compared with the pure polyamide system without adding the flame retardant.

[0021] 2. The covalent organic framework material (COFs) flame-retardant polyamide resin sheet has the advantages of high flame-retardant performance, no phosphorus addition, good mechanical properties, high transparency and the like. The elongation at break is more than 350%, the vertical burning level reaches the UL94 V-0 level, and the peak value of the heat release rate of the cone calorimeter is lower than 340 kW / m 2 , and the fire risk is greatly reduced.

[0022] 3. The covalent organic framework material (COFs) flame-retardant polyamide resin sheet of the present application can improve the char forming property of the polyamide resin, reduce the heat release rate and smoke release amount of the substrate, and strive for more fire evacuation time. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 Schematic diagram of PA6 and MTM / PA6 sheet composite; DETAILED DESCRIPTION

[0024] In order to further explain the present application, so that the advantages and characteristics of the present application can be more easily understood, the present application will be described in detail below through specific examples.

[0025] Comparative Example

[0026] Weigh 998 g of PA6 (Jiangsu Ruimei Fu, MF-700), 1 g of antioxidant 1010 (BASF Corporation), and 1 g of antioxidant 168 (BASF Corporation). Dry in a vacuum oven at 110°C for 5 hours for standby, double screw extruder speed 50 r / min (German Brabender reaction type extruder, screw diameter 20 mm), temperature setting: zone 1 245°C, zone 2 245°C, zone 3 250°C, zone 4 250°C, zone 5 250°C, die temperature 245°C. Add the uniformly mixed raw materials to the double screw extruder, cool, granulate, and injection mold the whole thickness of the measured sample to be 0.8 mm. LOI is 22.6%, UL94 V-2 level, heat release rate peak 526 kW / m 2 , total smoke release amount 103 m 2 / m 2 , elongation at break 332%.

[0027] Example 1

[0028] Weigh 978 g of PA6 (Jiangsu Ruimei Fu, MF-700), 20 g of MTM (laboratory self-made), 1 g of antioxidant 1010 (BASF Corporation), and 1 g of antioxidant 168 (BASF Corporation). Dry in a vacuum oven at 110°C for 5 hours for standby, internal mixer speed 40 r / min (Shanghai Kechuang XSS-300), temperature 280°C. Add the uniformly mixed raw materials to the internal mixer for blending, and press the sheet for standby. LOI is 28.3%, UL94 V-2 level, heat release rate peak 332 kW / m 2 , total smoke release amount 91 m 2 / m 2 , elongation at break 350%.

[0029] Example 2

[0030] Example 1 958 g PA6 (Jiangsu Ruimei Fu, MF-700), 40 g MTM (laboratory self-made), 1 g antioxidant 1010 (BASF), 1 g antioxidant 168 (BASF) were weighed. Dried in a vacuum oven at 110°C for 5 hours for standby, the speed of twin-screw extruder was 50 r / min (German Brabender reaction type extruder, screw diameter 20 mm), temperature setting: zone 1 245°C, zone 2 245°C, zone 3 250°C, zone 4 250°C, zone 5 250°C, head temperature 245°C. The uniformly premixed raw materials were added to the twin-screw extruder, cooled, granulated, and injection molded into the sample to be tested with a total thickness of 0.8 mm. The LOI was 32.1%, UL94 V-0 level, the peak heat release rate was 287 kW / m 2 , the total smoke release amount was 76 m 2 / m 2 , and the elongation at break was 368%.

[0031] Example 3

[0032] 938 g PA6 (Jiangsu Ruimei Fu, MF-700), 60 g MTM (laboratory self-made), 1 g antioxidant 1010 (BASF), 1 g antioxidant 168 (BASF) were weighed. Dried in a vacuum oven at 110°C for 5 hours for standby, the speed of twin-screw extruder was 50 r / min (German Brabender reaction type extruder, screw diameter 20 mm), temperature setting: zone 1 245°C, zone 2 245°C, zone 3 250°C, zone 4 250°C, zone 5 250°C, head temperature 245°C. The uniformly premixed raw materials were added to the twin-screw extruder, cooled, granulated, and injection molded into the sample to be tested with a total thickness of 0.8 mm. The LOI was 35.3%, UL94 V-0 level, the peak heat release rate was 247 kW / m 2 , the total smoke release amount was 48 m 2 / m 2 , and the elongation at break was 377%.

[0033] The above merely provides a specific implementation of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can think of changes or replacements within the technical range disclosed by the present application without creative labor, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be limited by the protection scope defined in the claims.

Claims

1. A covalent organic framework material (COFs) flame retardant polyamide resin sheet, characterized by: The component comprises the following components and mass percentage: polyamide 60-98%, MTM 2-15%, antioxidant 1010 0.1-1%, and antioxidant 168 0.1-1%. The component further comprises other auxiliary agents, and the addition amount of the other auxiliary agents is not more than 0.5% of the total mass of the component. The other auxiliary agent is at least one of an anti-dripping agent, a thermal stabilizer, a plasticizer, and a crosslinking agent. The MTM is 。 2. The flame retardant polyamide resin sheet of covalent organic frameworks (COFs) according to claim 1, characterized in that: The polyamide is one or a mixture of several of PA6, PA66, PA11, PA1212, PA46, PA610, PA612, and PA1010.

3. Process for the production of a flame-retardant polyamide resin sheet of covalent organic frameworks COFs according to claim 1 or 2, characterized in that: The raw materials are uniformly mixed and added to a blending device for melt blending; under the melting condition of the polyamide, the materials are extruded by using a screw extruder, and then pelletized, and after collection, the materials are added to an injection molding machine for injection molding under the melting condition of the polyamide.

4. A method of producing a flame-retardant polyamide resin sheet of a covalent organic framework material COF as claimed in claim 1 or 2, characterized by: The polyamide is heated to a melting state in a banbury mixer or an open mill, and then other necessary materials are gradually added, the uniformly mixed materials are broken and pelletized to obtain the required flame-retardant polyamide resin particles, and after collection, the particles are added to an injection molding machine for injection molding under the melting condition of the polyamide.

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