High-temperature-resistant flame-retardant flexible container bag material and preparation method thereof

Abstract

The invention relates to a high-temperature-resistant flame-retardant flexible container bag material and a preparation method thereof.The high-temperature-resistant flame-retardant flexible container bag material is prepared from 100-120 parts of polypropylene, 12-16 parts of composite nanofiller and 1-3 parts of antioxidant, and the composite nanofiller is prepared from modified calcium carbonate, halloysite nanotube slow-release matter and composite graphene; the modified calcium carbonate raw materials comprise oleic acid, a maleic acid-propylene copolymer and calcium carbonate. The flame-retardant flexible freight bag material has the effect of improving the flame-retardant property of the flexible freight bag material.

Description

Technical Field

[0001] The present application relates to the field of packaging materials, and in particular to a high temperature resistant and flame retardant flexible container bag material and a preparation method thereof. Background Art

[0002] Container bags, also known as flexible container bags, ton bags, space bags, etc., are a kind of flexible transport packaging container. They are widely used in the transportation and packaging of powdered, granular, and blocky items such as food, grains, medicines, chemicals, and minerals.

[0003] With the rapid development of industry, the demand for bulk bags is increasing. Polypropylene, as the raw material of bulk bags, is an organic high molecular compound with a low limiting oxygen index. It is easy to burn when encountering open flames, high temperatures and other fire sources in the air, and may spread rapidly, causing danger, so it needs to be improved. Summary of the invention

[0004] In order to further improve the flame retardant properties of bulk bags, the present application provides a high temperature resistant flame retardant flexible bulk bag material and a preparation method thereof.

[0005] In the first aspect, the present application provides a high temperature resistant and flame retardant flexible container bag material, which adopts the following technical scheme: a high temperature resistant and flame retardant flexible container bag material, comprising 100-120 parts of polypropylene, 12-16 parts of composite nanofiller, and 1-3 parts of antioxidant, wherein the composite nanofiller comprises modified calcium carbonate, halloysite nanotube sustained release and composite graphene, and the modified calcium carbonate raw material comprises oleic acid, maleic acid-propylene copolymer and calcium carbonate.

[0006] By adopting the above technical scheme, a composite nanofiller is added to the system, which can further improve the overall stability of the container bag material system. The composite nanofiller includes modified calcium carbonate, halloysite nanotube sustained-release material and composite graphene. The calcium carbonate modified by oleic acid and maleic acid-propylene copolymer can further improve the overall strength of the system. In addition, calcium carbonate has good high temperature resistance, which can improve the high temperature resistance of the container bag material, and also has good flame retardant properties. It will absorb a large amount of heat when decomposed by heat, and release carbon dioxide gas, which plays a role in isolating the air, thereby playing a flame retardant role.

[0007] Preferably, the modified calcium carbonate is prepared by the following method: Calcium carbonate is mixed with anhydrous ethanol to obtain a calcium carbonate dispersion, oleic acid is mixed with anhydrous ethanol, and added to the calcium carbonate dispersion to react to obtain a composite, maleic acid-propylene copolymer is mixed with water, and then added to the mixture, and after the reaction, the mixture is washed and dried to obtain modified calcium carbonate.

[0008] By adopting the above technical scheme, oleic acid and maleic acid-propylene copolymer are used to carry out composite modification on the surface of calcium carbonate, the carboxyl groups in oleic acid can react with the hydroxyl groups on the surface of calcium carbonate to form chemical bonds, so as to achieve the coating effect on calcium carbonate, and at the same time, the maleic acid-propylene copolymer has a good dispersing effect on carbonates, and a large number of carboxyl groups on the surface can react with the hydroxyl groups on the surface of calcium carbonate, so that the particle size of the modified calcium carbonate is more uniform, can be evenly dispersed in the system, and has good compatibility in the system, and the overall strength of the system is also improved.

[0009] Preferably, the mass ratio of the calcium carbonate, oleic acid and maleic acid-propylene copolymer is 1:(0.03-0.05):0.02.

[0010] By adopting the above technical solution, the mass ratio of calcium carbonate, oleic acid and maleic acid-propylene copolymer is preferably within the above range, which can further improve the overall stability of the prepared modified calcium carbonate.

[0011] Preferably, the halloysite nanotube sustained-release material comprises halloysite nanotubes, decanoic acid and styrene.

[0012] By adopting the above technical scheme, halloysite nanotubes are a kind of multi-walled inorganic nanotubes formed by curling natural kaolin and have a cavity structure. Polystyrene is an excellent shell material with good ductility and good mechanical properties, and can stably coat the phase change material. Then, decanoic acid is used as the core material and halloysite nanotubes are used as the thermal conductor to prepare the halloysite nanotube sustained-release material, which has good heat storage performance, can suppress heat and smoke during combustion, and further improves the overall flame retardant performance of the system.

[0013] Preferably, the halloysite nanotube sustained-release material is prepared by the following method: A surfactant and capric acid are mixed with water and stirred to obtain an emulsion system; styrene, ethyl acrylate, ethylene glycol and methacrylate, ammonium persulfate and ferric sulfate heptahydrate are added to the emulsion system and stirred; sodium thiosulfate and tert-butyl hydroperoxide are then added, the mixture is filtered, washed and dried to obtain a microcapsule system; halloysite nanotubes are mixed with water, stirred in a water bath environment, and then added to the microcapsule system, ultrasonically dispersed, filtered, washed and dried to obtain a halloysite nanotube sustained-release material.

[0014] By adopting the above technical scheme, an organic phase change material with polystyrene as the shell and decanoic acid as the core material was successfully synthesized by emulsion polymerization, and the halloysite sustained-release material was modified by halloysite carbon nanotubes. The addition of halloysite nanotubes effectively improved the thermal stability of the organic phase change material, and it also has good reliability in high temperature environment. At the same time, the overall heat resistance of the system is also improved, and the overall flame retardant performance of the system can be improved.

[0015] Preferably, the mass ratio of decanoic acid, ethyl styrene acrylate and halloysite nanotubes is 2:1:(0.04-0.06).

[0016] By adopting the above technical solution, preferably the mass ratio of decanoic acid, ethyl styrene acrylate and halloysite nanotubes is within the above range, which can further improve the stability of the prepared halloysite nanotube sustained-release material.

[0017] Preferably, the composite graphene is prepared by the following method: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added to N,N-dimethylformamide and stirred to obtain a composite system, graphene oxide is added to N,N-dimethylformamide and ultrasonically dispersed to obtain a graphene oxide dispersion, the graphene oxide dispersion is added to the composite, stirred for reaction, and filtered under reduced pressure after the reaction, and then washed and dried to obtain composite graphene.

[0018] By adopting the above technical solution, graphene oxide has a two-dimensional crystalline carbon atom structure and has good in-plane thermal conductivity. It can improve the overall thermal conductivity of the material and is conducive to the rapid dissipation of heat, thereby improving the stability of the system in a high temperature environment. After being compounded with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the flame retardant properties of the system can be further improved, forming a continuous physical barrier on the surface of the material. When the material burns, it can prevent heat from being transferred to the inside of the material, slowing down the thermal decomposition rate of the material, and at the same time hindering the contact between oxygen and the material, inhibiting the continued reaction of combustion, thereby improving the overall heat resistance and flame retardant properties of the system.

[0019] Preferably, the composite nanofiller is prepared by the following method: The modified calcium carbonate is mixed with N,N-dimethylformamide and then ultrasonically dispersed to obtain a modified calcium carbonate dispersion; the halloysite nanotube sustained-release material is mixed with N,N-dimethylformamide and then ultrasonically dispersed to obtain a halloysite nanotube sustained-release material dispersion; the composite graphene is mixed with anhydrous ethanol and then ultrasonically dispersed to obtain a composite graphene dispersion; the composite graphene dispersion, the halloysite sustained-release material dispersion and the modified calcium carbonate dispersion are mixed, ultrasonically dispersed and centrifuged, washed, and freeze-dried to obtain a composite nanofiller.

[0020] By adopting the above technical solution, after the modified calcium carbonate, halloysite nanotube slow-release material and composite graphene are mixed, a stable network nanostructure can be formed, thereby further improving the overall stability and strength of the system, and the heat transfer performance of the system is also improved, further improving the overall thermal insulation performance of the container bag material.

[0021] Preferably, the mass ratio of the modified calcium carbonate, the halloysite nanotube sustained release material and the composite graphene is (1.2-1.4):1:0.83.

[0022] By adopting the above technical solution, the mass ratio between the modified calcium carbonate, the halloysite nanotube sustained release material and the composite graphene is preferably within the above range, which can further improve the overall stability of the system.

[0023] In the second aspect, the present application provides a method for preparing a high temperature resistant and flame retardant flexible container bag material, which adopts the following technical scheme: A method for preparing a high temperature resistant and flame retardant flexible container bag material comprises the following steps: The polypropylene, composite nano filler and antioxidant are mixed and sent into a twin-screw extruder. After being extruded by the twin-screw extruder, the mixture is dried and then injection molded by an injection molding machine to obtain a high temperature resistant and flame retardant flexible container bag material.

[0024] In summary, the present application includes at least one of the following beneficial technical effects: 1. A nanocomposite material is added to the system, and the nanocomposite material includes modified calcium carbonate, halloysite nanotube slow-release material and composite graphene. On the one hand, the overall strength of the system can be improved, and on the other hand, the nanocomposite material has good high temperature resistance. Among them, the modified calcium carbonate is prepared by oleic acid, maleic acid-propylene copolymer and calcium carbonate, which can further improve the overall particle size uniformity of calcium carbonate, and at the same time further improve the dispersion performance of maleic acid in the system, so as to improve the overall stability of the system; 2. An organic phase change material with polystyrene as the shell and decanoic acid as the core material is synthesized by emulsion polymerization. The halloysite sustained-release material is obtained by modification with halloysite nanotubes. Polystyrene has good ductility and good mechanical properties and can stably coat the phase change material. The halloysite nanotubes improve the thermal stability of the phase change material. Decanoic acid has high phase change latent heat and chemical stability. The prepared halloysite nanotube sustained-release material has good high temperature resistance and flame retardant properties. 3. Graphene oxide has a two-position crystalline carbon atom structure and has good in-plane thermal conductivity, which is beneficial to the rapid dissipation of heat in the system, thereby improving the overall heat resistance of the system. After graphene oxide is compounded with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the overall flame retardant properties of the system are further improved, further improving the overall heat resistance and flame retardant properties of the container bag material. DETAILED DESCRIPTION

[0025] The present application is further described in detail below with reference to the embodiments: Description of raw materials: All raw materials in the examples are commercially available; the oxidant is antioxidant T501; and the surfactant is octylphenol polyoxyethylene ether (CAS No.: 26636-32-8).

[0026] Example 1 Preparation of composite graphene: 70.24 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS No.: 35948-25-5) was added to 500 mL of N,N-dimethylformamide (CAS No.: 68-12-2), the temperature was raised to 60 ° C, and the mixture was stirred for 10 min to fully dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain a composite system. 9.76 g of graphene oxide was added to 300 mL of N,N-dimethylformamide and ultrasonically dispersed for 25 min to obtain a graphene oxide dispersion. The graphene oxide dispersion was added to the composite system, and the temperature was raised to 60 ° C and stirred for reaction for 7.5 h under a nitrogen protection atmosphere. After the reaction, the mixture was filtered under reduced pressure, and then washed repeatedly with N,N-dimethylformamide for 3 times, and then vacuum dried at -60 ° C for 10 h to obtain composite graphene.

[0027] Preparation of modified calcium carbonate: 20 g of calcium carbonate was mixed with 200 g of anhydrous ethanol to obtain a calcium carbonate dispersion, 0.6 g of oleic acid (CAS No.: 112-80-1) was mixed with 20 g of anhydrous ethanol, added to the calcium carbonate dispersion, and reacted for 60 minutes to obtain a composite, 0.4 g of maleic acid-propylene copolymer (CAS No.: 25035-69-2) was mixed with 20 g of deionized water, and then added to the mixture. After reacting for 3 hours, it was cooled to 25°C, and then washed alternately with deionized water and anhydrous ethanol for 3 times, and finally dried in an oven at 80°C for 10 hours to obtain modified calcium carbonate.

[0028] Preparation of Halloysite Nanotube Sustained Release Material: 6.4 g of surfactant and 140 g of capric acid (CAS No.: 334-48-5) were added to 800 mL of deionized water, and stirred at 1200 rpm for 40 min in a 40°C water bath to obtain an emulsion system. Then 70 g of styrene (CAS No.: 100-42-5), 70 g of ethyl acrylate (CAS No.: 140-88-5), 40 g of ethylene glycol dimethacrylate (CAS No.: 97-90-5), 1.25 g of ammonium persulfate and 5 g of ferric sulfate heptahydrate were added to the emulsion system and continued to stir. 30min, then add 1.25g of sodium thiosulfate and 5g of tert-butyl hydroperoxide (CAS No.: 75-91-2), then heat the system to 95°C, filter, wash and dry with anhydrous ethanol to obtain a microcapsule system; 5.6g of halloysite nanotubes are added to 150g of deionized water, stirred at 2000rpm in a 40°C water bath for 27min, then added to the microcapsule system, ultrasonically dispersed for 15min, filtered and washed, and freeze-dried at -40°C for 18h to obtain a halloysite nanotube sustained-release material.

[0029] Preparation of composite nanofillers: 11.88 g of modified calcium carbonate was mixed with 200 g of N,N-dimethylformamide, and then ultrasonically dispersed for 5 minutes to obtain a modified calcium carbonate dispersion; 9.9 g of halloysite nanotube sustained-release material was mixed with 200 g of N,N-dimethylformamide, and then ultrasonically dispersed for 5 minutes to obtain a halloysite nanotube sustained-release material dispersion; 8.22 g of composite graphene was mixed with 200 g of anhydrous ethanol, and then ultrasonically dispersed for 10 minutes to obtain a composite graphene dispersion; the composite graphene dispersion, the halloysite sustained-release material dispersion and the modified calcium carbonate dispersion were mixed, ultrasonically dispersed and then centrifuged, washed with ethanol, and freeze-dried at -20°C for 8 hours to obtain a composite nanofiller.

[0030] Preparation of high temperature resistant and flame retardant flexible container bag materials: 100g of polypropylene, 12g of composite nanofiller and 1g of antioxidant are mixed and sent into a twin-screw extruder. After being extruded by the twin-screw extruder, the mixture is dried and then injection molded using an injection molding machine to obtain a high temperature resistant and flame retardant flexible container bag material.

[0031] Example 2 Preparation of composite graphene: 70.7 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added to 500 mL of N,N-dimethylformamide, the temperature was raised to 60° C., and the mixture was stirred for 10 min to fully dissolve the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain a composite system. 9.3 g of graphene oxide was added to 300 mL of N,N-dimethylformamide and ultrasonically dispersed for 25 min to obtain a graphene oxide dispersion. The graphene oxide dispersion was added to the composite system, the temperature was raised to 60° C. and the mixture was stirred for reaction for 7.5 h under a nitrogen protection atmosphere. After the reaction, the mixture was filtered under reduced pressure, washed repeatedly with N,N-dimethylformamide for 3 times, and then vacuum dried at -60° C. for 10 h to obtain a composite graphene.

[0032] Preparation of modified calcium carbonate: 20 g of calcium carbonate was mixed with 200 g of anhydrous ethanol to obtain a calcium carbonate dispersion, 1 g of oleic acid was mixed with 20 g of anhydrous ethanol, added to the calcium carbonate dispersion, and reacted for 60 minutes to obtain a composite, 0.4 g of maleic acid-propylene copolymer was mixed with 20 g of deionized water, and then added to the mixture. After reacting for 3 hours, it was cooled to 25°C, and then washed alternately with deionized water and anhydrous ethanol for 3 times, and finally dried in an oven at 80°C for 10 hours to obtain modified calcium carbonate.

[0033] Preparation of Halloysite Nanotube Sustained Release Material: 6.4 g of surfactant and 140 g of capric acid were added to 800 mL of deionized water, and stirred at 1200 rpm for 40 min in a water bath at 40° C. to obtain an emulsion system. Then 70 g of styrene, 70 g of ethyl acrylate, 40 g of ethylene glycol dimethacrylate, 1.25 g of ammonium persulfate and 5 g of ferric sulfate heptahydrate were added to the emulsion system and stirred for 30 min. Then 1.25 g of sodium thiosulfate and 5 g of tert-butyl hydroperoxide were added, and the system was heated to 95° C., filtered, washed and dried with anhydrous ethanol to obtain a microcapsule system. 8.4 g of halloysite nanotubes were added to 150 g of deionized water, stirred at 2000 rpm for 27 min in a water bath at 40° C., and then added to the microcapsule system, ultrasonically dispersed for 15 min, filtered and washed, and freeze-dried at a temperature of -40° C. for 18 h to obtain a halloysite nanotube sustained-release material.

[0034] Preparation of composite nanofillers: 13 g of modified calcium carbonate was mixed with 200 g of N,N-dimethylformamide, and ultrasonically dispersed for 5 minutes to obtain a modified calcium carbonate dispersion; 9.29 g of halloysite nanotube sustained-release material was mixed with 200 g of N,N-dimethylformamide, and ultrasonically dispersed for 5 minutes to obtain a halloysite nanotube sustained-release material dispersion; 7.71 g of composite graphene was mixed with 200 g of anhydrous ethanol and ultrasonically dispersed for 10 minutes to obtain a composite graphene dispersion; the composite graphene dispersion, the halloysite sustained-release material dispersion and the modified calcium carbonate dispersion were mixed, ultrasonically dispersed and then centrifuged, washed with ethanol, and freeze-dried at -20°C for 8 hours to obtain a composite nanofiller.

[0035] Preparation of high temperature resistant and flame retardant flexible container bag materials: 120 g of polypropylene, 16 g of composite nanofiller and 3 g of antioxidant were mixed and sent into a twin-screw extruder. After being extruded by the twin-screw extruder, the mixture was dried and then injection molded using an injection molding machine to obtain a high temperature resistant and flame retardant flexible container bag material.

[0036] Example 3 Preparation of composite graphene: 70.48 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added to 500 mL of N,N-dimethylformamide, the temperature was raised to 60° C., and the mixture was stirred for 10 min to fully dissolve the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain a composite system. 9.52 g of graphene oxide was added to 300 mL of N,N-dimethylformamide and ultrasonically dispersed for 25 min to obtain a graphene oxide dispersion. The graphene oxide dispersion was added to the composite system, the temperature was raised to 60° C. and the mixture was stirred for reaction for 7.5 h under a nitrogen protection atmosphere. After the reaction, the mixture was filtered under reduced pressure, washed repeatedly with N,N-dimethylformamide for 3 times, and then vacuum dried at -60° C. for 10 h to obtain a composite graphene.

[0037] Preparation of modified calcium carbonate: 20 g of calcium carbonate was mixed with 200 g of anhydrous ethanol to obtain a calcium carbonate dispersion, 0.8 g of oleic acid was mixed with 20 g of anhydrous ethanol, added to the calcium carbonate dispersion, and reacted for 60 minutes to obtain a composite, 0.4 g of maleic acid-propylene copolymer was mixed with 20 g of deionized water, and then added to the mixture. After reacting for 3 hours, it was cooled to 25°C, and then washed alternately with deionized water and anhydrous ethanol for 3 times, and finally dried in an oven at 80°C for 10 hours to obtain modified calcium carbonate.

[0038] Preparation of Halloysite Nanotube Sustained Release Material: 6.4 g of surfactant and 140 g of capric acid were added to 800 mL of deionized water, and stirred at 1200 rpm for 40 min in a water bath at 40° C. to obtain an emulsion system. Then 70 g of styrene, 70 g of ethyl acrylate, 40 g of ethylene glycol dimethacrylate, 1.25 g of ammonium persulfate and 5 g of ferric sulfate heptahydrate were added to the emulsion system and stirred for 30 min. Then 1.25 g of sodium thiosulfate and 5 g of tert-butyl hydroperoxide were added, and the system was heated to 95° C., filtered, washed and dried with anhydrous ethanol to obtain a microcapsule system. 7 g of halloysite nanotubes were added to 150 g of deionized water, stirred at 2000 rpm for 27 min in a water bath at 40° C., and then added to the microcapsule system, ultrasonically dispersed for 15 min, filtered and washed, and freeze-dried at a temperature of -40° C. for 18 h to obtain a halloysite nanotube sustained-release material.

[0039] Preparation of composite nanofillers: 12.46 g of modified calcium carbonate was mixed with 200 g of N,N-dimethylformamide, and then ultrasonically dispersed for 5 minutes to obtain a modified calcium carbonate dispersion; 9.58 g of halloysite nanotube sustained-release material was mixed with 200 g of N,N-dimethylformamide, and then ultrasonically dispersed for 5 minutes to obtain a halloysite nanotube sustained-release material dispersion; 7.96 g of composite graphene was mixed with 200 g of anhydrous ethanol and then ultrasonically dispersed for 10 minutes to obtain a composite graphene dispersion; the composite graphene dispersion, the halloysite sustained-release material dispersion and the modified calcium carbonate dispersion were mixed, ultrasonically dispersed and then centrifuged, washed with ethanol, and freeze-dried at -20°C for 8 hours to obtain a composite nanofiller.

[0040] Preparation of high temperature resistant and flame retardant flexible container bag materials: 110 g of polypropylene, 14 g of composite nanofiller and 2 g of antioxidant were mixed and sent to a twin-screw extruder. After being extruded by the twin-screw extruder, the mixture was dried and then injection molded using an injection molding machine to obtain a high temperature resistant and flame retardant flexible container bag material.

[0041] Example 4 Example 4 is based on Example 3. The difference between Example 4 and Example 3 is that in Example 4, 2.8 g of halloysite nanotubes are used when preparing the sustained-release halloysite nanotube material.

[0042] Example 5 Example 5 is based on Example 3. The difference between Example 5 and Example 3 is that in Example 5, 11.2 g of halloysite nanotubes are used when preparing the sustained-release halloysite nanotube material.

[0043] Example 6 Example 6 is based on Example 3. The difference between Example 6 and Example 3 is that in Example 6, when preparing composite graphene, 10.53 g of graphene oxide and 69.47 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are used.

[0044] Example 7 Example 7 is based on Example 3. The difference between Example 7 and Example 3 is that in Example 7, when preparing composite graphene, 8.7 g of graphene oxide and 71.3 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are used.

[0045] Example 8 Example 8 is based on Example 3. The difference between Example 8 and Example 3 is that in Example 8, 0.2 g of oleic acid is used when preparing modified calcium carbonate.

[0046] Example 9 Example 9 is based on Example 3. The difference between Example 9 and Example 3 is that in Example 9, 1.4 g of oleic acid is used when preparing modified calcium carbonate.

[0047] Example 10 Example 10 is based on Example 3. The difference between Example 10 and Example 3 is that in Example 10, when preparing the composite nanofiller, 10.6 g of modified calcium carbonate, 10.6 g of halloysite nanotube sustained release material and 8.8 g of composite graphene are added.

[0048] Embodiment 11 Example 11 is based on Example 3. The difference between Example 11 and Example 3 is that in Example 11, when preparing the composite nanofiller, 13.99 g of modified calcium carbonate, 8.75 g of halloysite nanotube sustained release material, and 7.26 g of composite graphene are added.

[0049] Example 12 Example 12 is based on Example 3, and in Example 12, no maleic acid-propylene copolymer is added when preparing modified calcium carbonate.

[0050] Example 13 Example 13 is based on Example 3. In Example 13, when preparing the composite nanofiller, the composite graphene is replaced with ordinary graphene oxide.

[0051] Embodiment 14 Example 14 is based on Example 3, and in Example 14, the halloysite nanotube sustained-release material in the composite nanofiller is replaced with ordinary halloysite nanotubes.

[0052] Comparative Example 1 Comparative Example 1 is based on Example 3. In Comparative Example 1, no halloysite nanotube sustained-release material is added when preparing the composite nanofiller.

[0053] Comparative Example 2 Comparative Example 2 is based on Example 3. In Comparative Example 2, no composite graphene is added when preparing the composite nanofiller.

[0054] Comparative Example 3 Comparative Example 3 is based on Example 3. In Comparative Example 3, no modified calcium carbonate is added when preparing the composite nanofiller.

[0055] Performance testing The following performance tests were performed on the samples of Examples 1-14 and Comparative Examples 1-3: (1) Flame retardant performance test The flame retardant properties of the samples were tested according to GB / T 2406-1993. Each sample was tested 3 times, and the average value was taken. The test results were filled in Table 1.

[0056] (2) Tensile strength test With reference to GB / T 8947-1998, the tensile strength of the conductive flat wire prepared from each sample was tested, and the test results were filled in Table 1.

[0057] Table 1 Performance test results of Examples 1-14 and Comparative Examples 1-3 Test items Limiting oxygen index / % Tensile strength g / d Example 1 38.0 4.62 Example 2 37.6 4.60 Example 3 38.4 4.65 Example 4 35.1 4.41 Example 5 34.7 4.38 Example 6 33.2 4.37 Example 7 33.7 4.32 Example 8 34.2 4.32 Example 9 34.1 4.34 Example 10 33.8 4.39 Embodiment 11 34.0 4.38 Example 12 33.2 4.27 Example 13 31.7 4.24 Embodiment 14 33.1 4.30 Comparative Example 1 28.5 4.02 Comparative Example 2 28.1 4.06 Comparative Example 3 28.3 4.01 Combined with Table 1, it can be seen that the limiting oxygen index of Examples 1-3 is 37.6% or above, indicating that the container bag material prepared in the present application has good flame retardant properties; the tensile strength of Examples 1-3 is 4.60g / d or above, indicating that the container bag material prepared in the present application has good mechanical strength.

[0058] In Examples 4 and 5, when preparing the sustained-release halloysite nanotubes, the mass ratios of halloysite nanotubes, decanoic acid and styrene are not within the range specified in the present application. When the content of the halloysite nanotubes is too little, it is difficult to further load the profile and the shell material, and the phase change material is free in the system, which reduces the stability of the prepared phase change material and affects the overall performance of the system. When the content of the halloysite nanotubes decreases, the overall flame retardant properties of the system are also affected. When the content of the halloysite nanotubes is too much, agglomeration will occur in the system, thereby affecting the overall stability of the system. Therefore, the performance of Examples 4 and 5 are both reduced.

[0059] In Example 6, when preparing composite graphene, the content of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is too little, the grafting rate is reduced, and the overall flame retardant properties of the system are affected. Therefore, the flame retardant properties of Example 6 are reduced; in Example 7, when preparing composite graphene, the content of graphene oxide is too little, which reduces the content of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide grafted with graphene oxide in the system, and also affects the overall flame retardant properties of the system. Therefore, the flame retardant properties of Example 7 are reduced.

[0060] In Example 8 and Example 9, when preparing modified calcium carbonate, the mass ratios of calcium carbonate, oleic acid and maleic acid-propylene copolymer are not within the range specified in the present application. When the content of oleic acid is too little, it is difficult to further promote the activation improvement of the surface of calcium carbonate by oleic acid, resulting in decreased compatibility and stability of calcium carbonate in the system. When the content of oleic acid is too high, excess oleic acid forms a double-layer structure on the surface of calcium carbonate, resulting in decreased particle size uniformity and stability of the system as a whole. Therefore, the performance of Example 8 and Example 9 are both reduced.

[0061] When preparing composite nanofillers in Examples 10 and 11, the mass ratios of modified calcium carbonate, halloysite nanotube sustained release material and composite graphene are not within the range specified in the present application, indicating that changing the mass ratio between the components will affect the overall comprehensive performance of the system, so the performance of Examples 10 and 11 are both reduced.

[0062] In Example 12, no maleic acid-propylene copolymer was added, and the dispersibility and compatibility of calcium carbonate not modified by maleic acid-propylene were reduced, and it was difficult to further enhance the synergistic effect of the system, so the performance of Example 12 was reduced.

[0063] In Example 13, the composite graphene was replaced with ordinary graphene oxide, and the flame retardant properties and thermal stability of the graphene oxide that had not been grafted and loaded were reduced.

[0064] In Example 14, the halloysite nanotube sustained-release material is replaced with ordinary halloysite nanotubes. The thermal stability of the halloysite sustained-release material without phase change material is difficult to further improve, and the compatibility is reduced, so the performance of Example 14 is reduced.

[0065] In Comparative Example 1, no halloysite nanotube sustained-release material was added, in Comparative Example 2, no composite graphene was added, and in Comparative Example 3, no modified calcium carbonate was added. Only two components were compounded, which reduced the synergistic performance of the system.

[0066] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of ​​the present application. The technical scope of the present application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A high temperature resistant and flame retardant flexible container bag material, characterized by: The invention comprises 100-120 parts of polypropylene, 12-16 parts of composite nanofiller and 1-3 parts of antioxidant. The composite nanofiller comprises modified calcium carbonate, halloysite nanotube slow-release material and composite graphene. The modified calcium carbonate raw material comprises oleic acid, maleic acid-propylene copolymer and calcium carbonate.

2. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The modified calcium carbonate is prepared by the following method: Calcium carbonate is mixed with anhydrous ethanol to obtain a calcium carbonate dispersion, oleic acid is mixed with anhydrous ethanol, and added to the calcium carbonate dispersion to react to obtain a composite, maleic acid-propylene copolymer is mixed with water, and then added to the mixture, and after the reaction, the mixture is washed and dried to obtain modified calcium carbonate.

3. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The mass ratio of the calcium carbonate, oleic acid and maleic acid-propylene copolymer is 1:(0.03-0.05):0.

02.

4. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The halloysite nanotube sustained-release material comprises halloysite nanotubes, decanoic acid and styrene.

5. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The halloysite nanotube sustained-release material is prepared by the following method: A surfactant and capric acid are mixed with water and stirred to obtain an emulsion system; styrene, ethyl acrylate, ethylene glycol and methacrylate, ammonium persulfate and ferric sulfate heptahydrate are added to the emulsion system and stirred; sodium thiosulfate and tert-butyl hydroperoxide are then added, the mixture is filtered, washed and dried to obtain a microcapsule system; halloysite nanotubes are mixed with water, stirred in a water bath environment, and then added to the microcapsule system, ultrasonically dispersed, filtered, washed and dried to obtain a halloysite nanotube sustained-release material.

6. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The mass ratio of the decanoic acid, styrene-ethyl acrylate and halloysite nanotubes is 2:1:(0.04-0.06).

7. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The composite graphene is prepared by the following method: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added to N,N-dimethylformamide and stirred to obtain a composite system, graphene oxide is added to N,N-dimethylformamide and ultrasonically dispersed to obtain a graphene oxide dispersion, the graphene oxide dispersion is added to the composite, stirred for reaction, and filtered under reduced pressure after the reaction, and then washed and dried to obtain composite graphene.

8. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The composite nanofiller is prepared by the following method: The modified calcium carbonate is mixed with N,N-dimethylformamide and then ultrasonically dispersed to obtain a modified calcium carbonate dispersion; the halloysite nanotube sustained-release material is mixed with N,N-dimethylformamide and then ultrasonically dispersed to obtain a halloysite nanotube sustained-release material dispersion; the composite graphene is mixed with anhydrous ethanol and then ultrasonically dispersed to obtain a composite graphene dispersion; the composite graphene dispersion, the halloysite sustained-release material dispersion and the modified calcium carbonate dispersion are mixed, ultrasonically dispersed and centrifuged, washed, and freeze-dried to obtain a composite nanofiller.

9. The high temperature resistant and flame retardant flexible container bag material according to claim 1, characterized in that: The mass ratio of the modified calcium carbonate, the halloysite nanotube sustained release material and the composite graphene is (1.2-1.4):1:0.

83.

10. A method for preparing the high temperature resistant and flame retardant flexible container bag material according to any one of claims 1 to 9, characterized in that: The invention comprises the following preparation method: The polypropylene, composite nano filler and antioxidant are mixed and sent into a twin-screw extruder. After being extruded by the twin-screw extruder, the mixture is dried and then injection molded by an injection molding machine to obtain a high temperature resistant and flame retardant flexible container bag material.