CN110698772A - Modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material - Google Patents

Modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material Download PDF

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CN110698772A
CN110698772A CN201910979223.XA CN201910979223A CN110698772A CN 110698772 A CN110698772 A CN 110698772A CN 201910979223 A CN201910979223 A CN 201910979223A CN 110698772 A CN110698772 A CN 110698772A
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ammonium polyphosphate
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郑玉婴
于文泰
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2207/04—Thermoplastic elastomer

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Abstract

The invention discloses a modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material and a preparation method thereof, wherein the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material comprises the following raw materials in parts by weight: 100 parts of rubber-plastic elastomer, 10-50 parts of compound flame retardant, 5-12 parts of naphthenic oil, 5-10 parts of superfine white carbon black, 3-5 parts of hydrated lime, 1-2 parts of zinc stearate, 100 parts of calcium carbonate and 130 parts of plastic toner; in the compound flame retardant, the mass ratio of the modified ammonium polyphosphate to the modified graphene oxide is 1-5: 1. the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material prepared by the invention has the characteristics of good flame-retardant effect, aging resistance, high tensile strength and the like, and has wide application prospect and market demand.

Description

Modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material
Technical Field
The invention belongs to the technical field of plastic runways, and particularly relates to a modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material and a preparation method thereof.
Background
The plastic track is an indispensable important facility in the modern track and field ground and has been set as one of the necessary conditions of the international competition ground by the international organization for Olympic Commission. Compared with the traditional soil track, the novel soil track has the advantages of good elasticity, skid resistance, wear resistance and shock absorption, easy field nursing, bright color, beauty and orderliness. In view of the above advantages, plastic runways are soon being adopted by various track and field sites. However, the runway particles belong to flammable materials, and are easy to cause fire in the using process, so that the property and personal safety of people are greatly threatened, and therefore, the functional modification of the runway particles in the aspect of flame retardance is imperative.
At present, the halogen flame retardant occupies the dominant position of the rubber and plastic material flame retardant due to the excellent characteristics of high flame retardant efficiency, moderate price, multiple varieties, wide application range and the like, and is also a main method for improving the flame retardant performance. Although the halogen flame retardant has a very high flame retardant efficiency, it generates a large amount of corrosive gas such as hydrogen halide and smoke during thermal cracking or combustion. Once a fire disaster occurs, great difficulty is brought to escape and rescue personnel, death accidents can be caused in serious cases, and meanwhile, great threat is also formed to the environment. With the enhancement of the awareness of safety and environmental protection of people, the development of efficient, nontoxic and environment-friendly flame retardants becomes a requirement for the development of modern flame retardants.
Disclosure of Invention
The invention aims to provide a modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material and a preparation method thereof, aiming at the defects of the prior art. The modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material prepared by the invention has a good flame-retardant effect, the flame-retardant index of the material reaches UL94V0 level, and the material is free of halogen raw materials, so that the generated gas does not pollute the environment and has good processing performance and mechanical performance, and therefore, the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material has a wide application prospect and market requirements.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material comprises the following raw materials in parts by weight: 100 parts of rubber-plastic elastomer, 10-50 parts of compound flame retardant, 5-12 parts of naphthenic oil, 5-10 parts of superfine white carbon black, 3-5 parts of hydrated lime, 1-2 parts of zinc stearate, 100 parts of calcium carbonate and 130 parts of plastic toner.
The rubber-plastic elastomer comprises: polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), polyethylene, polypropylene, Ethylene Propylene Diene Monomer (EPDM), ethylene-vinyl acetate copolymer (EVA), polyethylene grafted maleic anhydride and thermoplastic polyurethane. The polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) is linear high molecular weight SEBS. The grafting rate of the polyethylene grafted maleic anhydride is 1.2%. The content of vinyl acetate matrix in the ethylene-vinyl acetate copolymer is 13-18 wt%.
The compound flame retardant takes modified ammonium polyphosphate as an acid source and an air source, modified graphene oxide as a carbon source, and the mass ratio of the modified ammonium polyphosphate to the modified graphene oxide is 1-5: 1.
The preparation method of the compound flame retardant comprises the following steps: dissolving 1 part of modified graphene oxide in deionized water, carrying out ultrasonic oscillation for 30min, then adding 1-5 parts of modified ammonium polyphosphate, stirring for 1h, washing, and then drying at 60 ℃.
The specific preparation method of the modified ammonium polyphosphate comprises the following steps: 1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min. 2) 5mL of absolute ethanol and 0.5mL of KH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 3.5-5.0. 3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate. 4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
The specific preparation method of the modified graphene oxide comprises the following steps: 1) GO is prepared from graphite powder by Hummers method. 2) 1gGO was immersed in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour. 3) Dissolve 1mLKH550 in GO slurry and stir well for 30 minutes. 4) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour. 5) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
A method for preparing the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material comprises the following specific steps:
1) weighing various required materials according to the requirements of the formula;
2) pouring the polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 20-30min at 50 ℃, and setting the rotating speed at 200-300 r/min.
3) Pouring the rest materials weighed in the step 1) into a high-speed mixer, and continuously mixing for 20-30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 400-600r/min, and extruding and granulating to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Ammonium polyphosphate (APP) is used as a halogen-free intumescent flame retardant common additive, has high P, N content and good performance in the flame retardant effect, and can be widely applied in the flame retardant field. Under the action of high temperature, APP is decomposed into polyphosphoric acid and ammonia gas, and the ammonia gas can play a role of a gas source and dilute oxygen; polyphosphoric acid serves as the acid source. But as a phosphate, the phosphate has poor compatibility and poor dispersibility in a polymer matrix, and an agglomeration phenomenon can occur; the moisture absorption is serious, and the amino group on the APP is easy to absorb moisture; the addition amount is large, and the material performance is influenced. The silane coupling agent KH550 contains good flame-retardant elements such as Si and N, and the KH550 is grafted to an APP structure, so that the flame-retardant property of the product can be improved, and the dispersion of the product in a system can be greatly promoted. The surface of GO has a large amount of hydroxyl, and the hydroxyl can provide a carbon source under the action of an acid source or by dehydration into carbon during combustion. And the added functionalized graphene oxide containing silicon and boron can serve as a carbon source and release non-combustible gas CO after being heated2、H2O for the interlamellar spacing grow, can strengthen the expanded carbon layer simultaneously, can form at fine protective layer on the material surface, thereby reinforcing and modified APP's synergism. But also improves the mechanical property, the thermal property and the air tightness of the runway particle material.
The invention has the beneficial effects that: the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material prepared by the invention has a good flame-retardant effect, the flame-retardant index of the material reaches UL94V0 level, and the material is free of halogen raw materials, so that the generated gas does not pollute the environment, and the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material has good processability and mechanical properties, thereby having wide application prospect and market demand.
Drawings
Fig. 1 is an infrared diagram of graphene oxide/modified graphene oxide/boric acid;
FIG. 2 is an SEM image of modified ammonium polyphosphate;
fig. 3 is an SEM image of graphene oxide.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The invention is further illustrated by the following examples.
Example 1
A method for preparing modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle materials comprises the following specific steps:
1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min.
2) 5mL of absolute ethanol and 0.5mL of KH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 5.0.
3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate.
4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
5) 1g of GO prepared by the Hummers method was soaked in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour.
6) 1mL KH550 was dissolved in GO slurry and stirred well for 30 minutes.
7) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour.
8) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
9) Dissolving 1 part of fGO in deionized water, ultrasonically oscillating for 30min, then adding 1 part of modified ammonium polyphosphate, stirring for 1h, washing, and then drying at 60 ℃ to obtain the compound flame retardant.
10) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 10 parts of a compound flame retardant, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
11) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
12) Pouring the rest of the weighed materials in the step 10) into a high-speed mixer, and continuously mixing for 30 min.
13) And transferring the mixed materials into a double-screw extruder, extruding and granulating at the temperature of 180-200 ℃ and the rotating speed of 600r/min in each zone to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Example 2
A method for preparing modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle materials comprises the following specific steps:
1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min.
2) 5mL of absolute ethanol and 0.5mL of KH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 5.0.
3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate.
4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
5) 1g of GO prepared by the Hummers method was soaked in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour.
6) 1mL KH550 was dissolved in GO slurry and stirred well for 30 minutes.
7) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour.
8) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
9) Dissolving 1 part of fGO in deionized water, ultrasonically oscillating for 30min, then adding 2 parts of modified ammonium polyphosphate, stirring for 1h, washing and then drying at 60 ℃. And preparing the compound flame retardant.
10) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 20 parts of a compound flame retardant, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
11) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
12) Pouring the rest of the weighed materials in the step 10) into a high-speed mixer, and continuously mixing for 30 min.
13) And transferring the mixed materials into a double-screw extruder, extruding and granulating at the temperature of 180-200 ℃ and the rotating speed of 600r/min in each zone to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Example 3
A method for preparing modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle materials comprises the following specific steps:
1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min.
2) 5mL of absolute ethanol and 0.5mL of KH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 5.0.
3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate.
4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
5) 1g of GO prepared by the Hummers method was soaked in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour.
6) 1mL KH550 was dissolved in GO slurry and stirred well for 30 minutes.
7) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour.
8) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
9) Dissolving 1 part of fGO in deionized water, ultrasonically oscillating for 30min, then adding 3 parts of modified ammonium polyphosphate, stirring for 1h, washing, and then drying at 60 ℃ to obtain the compound flame retardant.
10) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 30 parts of compound flame retardant, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
11) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
12) Pouring the rest of the weighed materials in the step 10) into a high-speed mixer, and continuously mixing for 30 min.
13) And transferring the mixed materials into a double-screw extruder, extruding and granulating at the temperature of 180-200 ℃ and the rotating speed of 600r/min in each zone to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Example 4
A method for preparing modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle materials comprises the following specific steps:
1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min.
2) 5mL of absolute ethanol and 0.5mL of LKH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 5.0.
3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate.
4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
5) 1g of GO prepared by the Hummers method was soaked in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour.
6) 1mL KH550 was dissolved in GO slurry and stirred well for 30 minutes.
7) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour.
8) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
9) Dissolving 1 part of fGO in deionized water, ultrasonically oscillating for 30min, then adding 4 parts of modified ammonium polyphosphate, stirring for 1h, washing, and then drying at 60 ℃ to obtain the compound flame retardant.
10) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 40 parts of a compound flame retardant, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
11) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
12) Pouring the rest of the weighed materials in the step 10) into a high-speed mixer, and continuously mixing for 30 min.
13) And transferring the mixed materials into a double-screw extruder, extruding and granulating at the temperature of 180-200 ℃ and the rotating speed of 600r/min in each zone to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Example 5
A method for preparing modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle materials comprises the following specific steps:
1) to a beaker containing 100mL of deionized water were added 15mL of absolute ethanol and 10g of ammonium polyphosphate, and the mixture was stirred at 70 ℃ for 30 min.
2) 5mL of absolute ethanol and 0.5mL of LKH550 were added to a beaker containing 50mL of deionized water, followed by dropwise addition of glacial acetic acid to adjust the pH to 5.0.
3) And dropwise adding the mixed solution into a mixed solution of ammonium polyphosphate and ethanol, and continuously stirring for 1h at 70 ℃ to obtain the modified ammonium polyphosphate.
4) Washing the modified ammonium polyphosphate obtained in the step 3) with absolute ethyl alcohol for a plurality of times, and drying in a vacuum oven at 70 ℃.
5) 1g of GO prepared by the Hummers method was soaked in 90% aqueous ethanol (100 mL) and treated with ultrasonic agitation at a temperature of 25 ℃ for 1 hour.
6) 1mL KH550 was dissolved in GO slurry and stirred well for 30 minutes.
7) 0.25g boric acid was slowly added to the GO slurry and the mixture was stirred at 25 ℃ for 1 hour.
8) The mixture was filtered with suction, washed with absolute ethanol and dried at 60 ℃ for 24 hours to give the final product fGO.
9) Dissolving 1 part of fGO in deionized water, ultrasonically oscillating for 30min, then adding 5 parts of modified ammonium polyphosphate, stirring for 1h, washing, and then drying at 60 ℃ to obtain the compound flame retardant.
10) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 50 parts of compound flame retardant, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
11) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
12) Pouring the rest of the weighed materials in the step 10) into a high-speed mixer, and continuously mixing for 30 min.
13) And transferring the mixed materials into a double-screw extruder, extruding and granulating at the temperature of 180-200 ℃ and the rotating speed of 600r/min in each zone to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
Comparative example 1
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 2
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 10 parts of modified ammonium polyphosphate, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 3
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 30 parts of modified ammonium polyphosphate, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 4
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 50 parts of modified ammonium polyphosphate, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of hydrated lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner in parts by weight.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 5
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 10 parts of modified graphene oxide, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of slaked lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 6
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 30 parts of modified graphene oxide, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of slaked lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Comparative example 7
1) Weighing 20 parts of polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS), 20 parts of thermoplastic polyurethane, 40 parts of Ethylene Propylene Diene Monomer (EPDM), 10 parts of polyethylene grafted maleic anhydride, 10 parts of polypropylene, 50 parts of modified graphene oxide, 12 parts of naphthenic oil, 5 parts of superfine white carbon black, 3 parts of slaked lime, 2 parts of zinc stearate, 100 parts of calcium carbonate and 0.5 part of plastic toner.
2) Pouring polystyrene-polyethylene-polybutylene-polystyrene block copolymer (SEBS) into a high-speed mixer, simultaneously pouring naphthenic oil, stirring and filling oil for 30min at 50 ℃, and setting the rotating speed at 200 r/min.
3) Pouring the rest of the weighed materials in the step 1) into a high-speed mixer, and continuously mixing for 30 min.
4) And transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 600r/min, and extruding and granulating to obtain the runway granular material.
Performance testing
Table 1 shows the flame retardant data of the modified ammonium polyphosphate/modified graphene oxide flame retardant runway particle material, and it can be seen from the table that, compared with comparative example 1 in which no flame retardant is added and comparative examples 2 to 7 in which only a single flame retardant is added, the flame retardant performance of the modified ammonium polyphosphate/modified graphene oxide flame retardant runway particle material prepared by the present invention is significantly improved, the oxygen index is 26.3% ~ 27.7.7%, which is significantly higher than that of comparative examples 1 to 7, the UL-94 rating is V-0, and the tensile strength is also improved to some extent, which indicates that the synergistic effect exists in the components of the compounded flame retardant.
Table 1 modified ammonium polyphosphate/modified graphene oxide flame retardant runway particulate material data
Figure DEST_PATH_IMAGE001
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. A modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material is characterized in that: the raw materials comprise the following components in parts by weight: 100 parts of rubber-plastic elastomer, 10-50 parts of compound flame retardant, 5-12 parts of naphthenic oil, 5-10 parts of superfine white carbon black, 3-5 parts of hydrated lime, 1-2 parts of zinc stearate, 100 parts of calcium carbonate and 130 parts of plastic toner; in the compound flame retardant, the mass ratio of the modified ammonium polyphosphate to the modified graphene oxide is 1-5: 1.
2. a fire retardant runway particulate material as defined in claim 1 wherein: the rubber-plastic elastomer comprises: one or more of polystyrene-polyethylene-polybutylene-polystyrene block copolymer, polyethylene, polypropylene, ethylene propylene diene monomer, ethylene-vinyl acetate copolymer, polyethylene grafted maleic anhydride and thermoplastic polyurethane.
3. A fire retardant runway particulate material as claimed in claim 2 wherein: the polystyrene-polyethylene-polybutylene-polystyrene block copolymer is linear high molecular weight SEBS, the grafting rate of polyethylene grafted maleic anhydride is 1.2%, and the content of a vinyl acetate matrix in the ethylene-vinyl acetate copolymer is 13-18 wt%.
4. A fire retardant runway particulate material as defined in claim 1 wherein: the preparation method of the compound flame retardant comprises the following steps: dissolving 1 part of modified graphene oxide in deionized water, carrying out ultrasonic oscillation for 30min, then adding 1-5 parts of modified ammonium polyphosphate, stirring for 1h, washing, and drying at 60 ℃.
5. A fire retardant runway particulate material as claimed in claim 4 wherein: the preparation method of the modified ammonium polyphosphate comprises the following steps:
1) adding 15mL of absolute ethyl alcohol and 10g of ammonium polyphosphate into 100mL of deionized water, and stirring for 30min at 70 ℃;
2) adding 5mL of absolute ethyl alcohol and 0.5mL of KH550 into 50mL of deionized water, then dropwise adding glacial acetic acid, and adjusting the pH value to 3.5-5.0;
3) dropwise adding the mixed solution obtained in the step 2) into the mixed solution obtained in the step 1), continuously stirring for 1h at 70 ℃, filtering, washing with absolute ethyl alcohol, and drying at 70 ℃ to obtain modified ammonium polyphosphate.
6. A fire retardant runway particulate material as claimed in claim 4 wherein: the preparation method of the modified graphene oxide comprises the following steps:
1) the graphene oxide is prepared by a Hummers method;
2) soaking 1g of graphene oxide in 100mL of 90 wt% ethanol solution, and ultrasonically stirring for 1 hour at 25 ℃; adding 1mLKH550, and fully stirring for 30 minutes; slowly adding 0.25g of boric acid, and stirring for 1 hour at 25 ℃; filtering, washing with absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain the modified graphene oxide.
7. A method for preparing the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material of claim 1, which is characterized in that: the method comprises the following specific steps:
1) adding rubber-plastic elastomer and naphthenic oil into a high-speed mixer, stirring at 50 ℃ and charging oil for 20-30min at the rotation speed of 200-300 r/min;
2) adding the rest raw materials, and mixing for 20-30 min;
3) and transferring the mixed materials into a double-screw extruder, wherein the temperature of each zone is 180-200 ℃, the rotating speed is 400-600r/min, and extruding and granulating to obtain the modified ammonium polyphosphate/modified graphene oxide flame-retardant runway granular material.
CN201910979223.XA 2019-10-15 2019-10-15 Modified ammonium polyphosphate/modified graphene oxide flame-retardant runway particle material Pending CN110698772A (en)

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