CN116284880A - Method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads from waste polystyrene - Google Patents
Method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads from waste polystyrene Download PDFInfo
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- CN116284880A CN116284880A CN202310265515.3A CN202310265515A CN116284880A CN 116284880 A CN116284880 A CN 116284880A CN 202310265515 A CN202310265515 A CN 202310265515A CN 116284880 A CN116284880 A CN 116284880A
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- Prior art keywords
- halogen
- free flame
- retardant
- flame retardant
- polystyrene
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 159
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 159
- 239000011324 bead Substances 0.000 title claims abstract description 149
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- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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Abstract
The invention relates to the technical field of high polymer materials, and provides a method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads by using waste polystyrene. According to the invention, a non-water-soluble composite halogen-free flame retardant and waste polystyrene are used as raw materials, the effective composition of the flame retardant and the polystyrene is realized by adopting a dissolution-distillation-suspension method, the halogen-free flame retardant polystyrene beads are prepared, and then the foaming agent is added to prepare the halogen-free flame retardant expandable polystyrene beads. The method provided by the invention has the advantages of simple process, energy conservation, emission reduction and environment friendliness, and the obtained halogen-free flame-retardant expandable polystyrene beads have excellent flame retardant property, solve the problems of white pollution caused by waste polystyrene and potential safety hazard caused by storage of polystyrene materials as inflammable materials, reduce the resource waste caused by the traditional treatment method and the consumption of a large amount of petroleum resources caused by the use for producing polystyrene, meet the national 'double carbon' strategic targets, and have wide prospects.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing halogen-free flame-retardant polystyrene beads and expandable polystyrene beads by using waste polystyrene.
Background
The polymer materials are widely applied to production and daily life, but most of the polymer materials are inflammable and have serious fire hazard. Polystyrene foam plastic is widely applied to production and life, is extremely easy to burn, releases toxic gas during combustion, and seriously endangers the life safety of users. The discarded polystyrene is extremely difficult to degrade, and causes white pollution. Therefore, the inflammability of polystyrene materials and the recovery and reuse of waste polystyrene are all problems to be solved.
Chinese patent CN113652075a discloses a halogen-free flame retardant composite material, a preparation method and application thereof, wherein thermoplastic polymer and functional auxiliary agent are added into a twin screw extruder to be extruded, and injection molding is performed in an injection molding machine to obtain the finished product. Chinese patent CN110922691a discloses a halogen-free flame-retardant polystyrene masterbatch and a preparation method thereof, wherein polystyrene resin, phosphorus flame retardant, antioxidant, toughening agent, flame retardant synergist, anti-dripping agent and lubricant are put into a high-speed mixer in proportion for dry mixing, and then are added into a twin-screw extruder for melting, mixing, extrusion, cooling, blow drying and granulation, thus obtaining the halogen-free flame-retardant polystyrene masterbatch. In addition, there is a report of preparing halogen-free flame-retardant polystyrene beads by suspension polymerization, in which a flame retardant is added during polymerization of styrene monomers, and in the research literature of mechanism of suspension polymerization, B.Kichatov et al, in Particle Size Distribution ofthe Product ofSuspension Polymerization, show that stability of a suspension polymerization system is a key to success of polymerization, and introduction of the flame retardant during suspension polymerization inevitably affects stability of the polymerization system, and polymerization retardation or even polymerization inhibition occurs.
In summary, the existing preparation method of the halogen-free flame-retardant polystyrene composite material mainly comprises copolymerization and blending. The method of using suspension polymerization requires selecting a flame retardant with high compatibility with styrene monomer to reduce negative effects on a suspension polymerization system, and the selection of the flame retardant is more severe; in the copolymerization and blending method, extrusion granulation is usually required, the extrusion granulation reaction condition is severe, the process parameters are complex, and toxic and harmful gases are released in the production. In addition, the patent or the literature adopts new polystyrene materials, and the recovery and the reutilization of waste polystyrene are not involved.
Therefore, it is currently needed to provide a preparation method of halogen-free flame-retardant polystyrene beads, which can realize the reutilization of waste polystyrene and is simple to operate.
Disclosure of Invention
In view of this, the present invention provides a method for preparing halogen-free flame retardant polystyrene beads and expandable polystyrene beads from waste polystyrene. The method provided by the invention takes the waste polystyrene as the raw material, has simple preparation method and easy operation, and can effectively solve the problems of environmental pollution caused by the waste polystyrene and potential safety hazard caused by taking the polystyrene as the inflammable material.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing halogen-free flame-retardant polystyrene beads by using waste polystyrene comprises the following steps:
mixing waste polystyrene, a composite halogen-free flame retardant, a dispersing agent, water and an organic solvent to obtain a mixed solution; the compound halogen-free flame retardant is obtained by compounding at least two halogen-free flame retardants; the halogen-free flame retardant is a phosphorus flame retardant, a nitrogen flame retardant or a nitrogen-phosphorus flame retardant; the halogen-free flame retardant is a water-insoluble flame retardant;
and (3) under the stirring condition, evaporating the organic solvent in the mixed solution to obtain the halogen-free flame-retardant polystyrene beads.
Preferably, the mixing comprises:
mixing waste polystyrene, a composite halogen-free flame retardant and an organic solvent to obtain a premix of the composite halogen-free flame retardant and the waste polystyrene;
mixing a dispersing agent and water to obtain a dispersing agent water solution;
and adding the dispersant aqueous solution into the premix of the composite halogen-free flame retardant and the waste polystyrene.
Preferably, the mass ratio of the waste polystyrene to the organic solvent is 1:2-10; the mass ratio of the waste polystyrene to the composite halogen-free flame retardant is 100:0.5-10;
The dispersing agent is a surfactant or a mixture of the surfactant and a water-soluble dispersing agent; when the dispersing agent is a surfactant, the mass fraction of the dispersing agent aqueous solution is 0.2-4.5%; when the dispersing agent is a mixture of a surfactant and a water-soluble dispersing agent, the total mass fraction of the surfactant and the water-soluble dispersing agent in the dispersing agent aqueous solution is 0.2-5%, wherein the mass fraction of the water-soluble dispersing agent is less than or equal to 0.5%;
the volume ratio of the dispersant aqueous solution to the premix of the composite halogen-free flame retardant and the waste polystyrene is 2-10:1.
Preferably, the compound halogen-free flame retardant comprises at least two of ammonium polyphosphate, hexaphenoxy cyclotriphosphazene, melamine polyphosphate, melamine cyanurate, melamine phytate, tripentaerythritol phosphate, tricresyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tolyldiphenyl phosphate, and tetraethyl N, N-p-phenylenediamine (2-hydroxy) dibenzylphosphonate;
the surfactant comprises one or more of sulfate, sulfonate, fatty acid salt, fatty alcohol polyoxyethylene ether sodium sulfate and terzorile; the water-soluble dispersing agent comprises one or more of alkyl cellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and alkylphenol ethoxylates;
The organic solvent comprises dichloromethane, acetone, methyl ethyl ketone, benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, butyl acetate, limonene or terpene.
Preferably, the distillation comprises a first stage distillation and a second stage distillation which are sequentially carried out; the temperature of the first-stage distillation is the boiling point temperature of the organic solvent, and the heat preservation time is 1-3 h; the temperature of the second-stage distillation is 15-30 ℃ above the boiling point of the organic solvent, and the heat preservation time is 0.5-4 h; the temperature rising rate from room temperature to the temperature of the first-stage distillation is 0.5-2 ℃/min; the temperature rising rate from the temperature of the first-stage distillation to the temperature of the second-stage distillation is 0.2-0.5 ℃/min.
The invention also provides the halogen-free flame-retardant polystyrene beads prepared by the method in the scheme, and the particle size of the halogen-free flame-retardant polystyrene beads is 0.5-3 mm.
The invention also provides a preparation method of the halogen-free flame-retardant expandable polystyrene beads, which comprises the following steps:
under a closed condition, mixing the halogen-free flame-retardant polystyrene beads and the surfactant aqueous solution, heating to 85-100 ℃, then adding a physical foaming agent, stirring at a constant temperature for 4-6 hours, and adding an inorganic dispersing agent into the system in the constant temperature stirring process;
And after the constant-temperature stirring is completed, cooling the obtained product liquid, and sequentially carrying out solid-liquid separation and drying to obtain the halogen-free flame-retardant expandable polystyrene beads.
Preferably, the mass fraction of the surfactant aqueous solution is 4-8%; the mass ratio of the halogen-free flame-retardant polystyrene beads to the surfactant aqueous solution is 1:1-4.
Preferably, the physical blowing agent comprises one or more of propane, butane, pentane, hexane, heptane, petroleum ether, freon 11 or freon 12; the mass of the physical foaming agent is 6-10% of the mass of the halogen-free flame-retardant polystyrene beads;
the inorganic dispersant comprises one or more of calcium phosphate, calcium hydroxy phosphate, calcium carbonate, calcium oxalate, barium sulfate, calcium sulfate, zinc oxide, magnesium hydroxide, aluminum hydroxide, bentonite, kaolin, titanium dioxide, graphite and mica; the mass of the inorganic dispersant is 0.1-8% of the mass of water in the system.
The invention also provides the halogen-free flame-retardant expandable polystyrene beads prepared by the preparation method of the scheme, and the particle size of the halogen-free flame-retardant expandable polystyrene beads is 0.5-3 mm.
The invention provides a method for preparing halogen-free flame-retardant polystyrene beads by using waste polystyrene, which comprises the following steps: mixing waste polystyrene, a composite halogen-free flame retardant, a dispersing agent, water and an organic solvent to obtain a mixed solution; the compound halogen-free flame retardant is obtained by compounding at least two halogen-free flame retardants; the halogen-free flame retardant is a phosphorus flame retardant, a nitrogen flame retardant or a nitrogen-phosphorus flame retardant; the halogen-free flame retardant is a water-insoluble flame retardant; and (3) under the stirring condition, evaporating the organic solvent in the mixed solution to obtain the halogen-free flame-retardant polystyrene beads. According to the invention, the halogen-free flame-retardant polystyrene beads are prepared by using the waste polystyrene as a raw material through a dissolution-distillation-suspension method, so that the halogen-free flame retardant and the polystyrene can be better compounded, the preparation process is simple, the large-scale production is easy, and the efficient recycling of the waste polystyrene is realized; the halogen-free flame retardant is adopted, so that the invention is safe and environment-friendly; in addition, the phosphorus flame retardant has high compatibility with polystyrene and an organic solvent, is not easy to adhere in the compounding process, and forms an intumescent flame retardant system in cooperation with the nitrogen flame retardant, so that the flame retardant effect is better than that of a single flame retardant; in addition, the halogen-free flame retardant selected by the invention is a water-insoluble flame retardant, and the water-insoluble flame retardant is compounded with polystyrene in an organic phase, so that the preparation of the halogen-free flame-retardant polystyrene beads is realized.
Furthermore, the organic solvent selected by the invention is a low-toxicity solvent, especially methylene dichloride, has the characteristics of non-inflammability, explosiveness, low boiling point, no toxicity and environmental protection, the adopted organic solvent can be recycled after being distilled, and the dispersing agent solution can also be recycled, so that the generation of waste liquid is avoided, the environment is better protected, and the preparation cost can be further reduced.
In conclusion, the invention solves the problem of white pollution caused by waste polystyrene and the problem of potential safety hazard caused by storage of polystyrene materials as inflammable materials, can also reduce the resource waste caused by the traditional treatment method and the consumption of a large amount of petroleum resources caused by the use of the polystyrene production, saves energy, reduces emission, is environment-friendly, and meets the national 'double-carbon' strategic targets.
The invention also provides a halogen-free flame-retardant expandable polystyrene bead which is prepared by adopting the scheme, a surfactant and a foaming agent, and the results of examples show that the halogen-free flame-retardant expandable polystyrene bead provided by the invention has excellent flame-retardant effect.
Drawings
FIG. 1 is a physical view of the halogen-free flame retardant polystyrene beads prepared in example 1 of the present invention.
FIG. 2 is a physical view of the halogen-free flame retardant polystyrene beads prepared in example 2 of the present invention.
FIG. 3 is a physical view of the halogen-free flame retardant polystyrene beads prepared in example 3 of the present invention.
FIG. 4 is a physical view of the halogen-free flame retardant polystyrene beads prepared in example 4 of the present invention.
FIG. 5 is a physical view of the halogen-free flame retardant polystyrene beads prepared in example 5 of the present invention.
FIG. 6 is a physical view of the halogen-free flame retardant polystyrene beads prepared in comparative example 1 of the present invention.
FIG. 7 is a physical view of the halogen-free flame retardant polystyrene beads prepared in comparative example 2 of the present invention.
Detailed Description
The invention provides a method for preparing halogen-free flame-retardant polystyrene beads by using waste polystyrene, which comprises the following steps:
mixing waste polystyrene, a composite halogen-free flame retardant, a dispersing agent, water and an organic solvent to obtain a mixed solution; the compound halogen-free flame retardant is obtained by compounding at least two halogen-free flame retardants; the halogen-free flame retardant is a phosphorus flame retardant, a nitrogen flame retardant or a nitrogen-phosphorus flame retardant; the halogen-free flame retardant is a water-insoluble flame retardant;
and (3) under the stirring condition, evaporating the organic solvent in the mixed solution to obtain the halogen-free flame-retardant polystyrene beads.
All the raw materials used in the present invention are commercially available unless otherwise specified.
The invention mixes waste polystyrene, composite halogen-free flame retardant, surfactant, water and organic solvent to obtain mixed solution. The invention has no special requirement on the waste polystyrene, and the common waste polystyrene products in the field can be used as raw materials of the invention, in particular, shockproof packaging materials such as valuables or fragile articles and packaging of fast food, and are cleaned and crushed before use. In the invention, the composite halogen-free flame retardant is obtained by compositing at least two halogen-free flame retardants; the halogen-free flame retardant is a phosphorus flame retardant, a nitrogen flame retardant or a nitrogen-phosphorus flame retardant, and is a water-insoluble flame retardant; specifically, the compound halogen-free flame retardant comprises at least two of ammonium polyphosphate, hexaphenoxy cyclotriphosphazene, melamine polyphosphate, melamine cyanurate, melamine phytate, tripentaerythritol phosphate, tricresyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tolyldiphenyl phosphate and tetraethyl N, N-p-phenylenediamine (2-hydroxy) dibenzyl phosphonate, preferably 2-3; in a specific embodiment of the present invention, the composite halogen-free flame retardant is preferably a composite of a phosphorus flame retardant and a nitrogen flame retardant, or a composite of a phosphorus flame retardant and a nitrogen phosphorus flame retardant, or a composite of a phosphorus flame retardant, a nitrogen flame retardant and a nitrogen flame retardant, more preferably a melamine cyanurate-triphenyl phosphate composite, a melamine polyphosphate-triphenyl phosphate composite, a hexaphenoxy cyclotriphosphazene-melamine cyanurate-triphenyl phosphate composite, a high ammonium polyphosphate-tripentaerythritol phosphate-triphenyl phosphate composite, or a melamine polyphosphate-melamine cyanurate-triphenyl phosphate composite; the mass ratio of the melamine cyanurate to the triphenyl phosphate in the melamine cyanurate-triphenyl phosphate compound is preferably 1:0.6-1.4, and more preferably 1:1; the mass ratio of the melamine polyphosphate to the triphenyl phosphate in the melamine polyphosphate-triphenyl phosphate compound is preferably 1:0.1-0.3, and more preferably 1:0.2; the mass ratio of hexaphenoxy cyclotriphosphazene, melamine cyanurate and triphenyl phosphate in the hexaphenoxy cyclotriphosphazene-melamine cyanurate-triphenyl phosphate compound is preferably 1:0.2-0.4:0.2-0.4, more preferably 3:1:1; the mass ratio of the high ammonium polyphosphate to the tripentaerythritol to the triphenyl phosphate in the high ammonium polyphosphate-tripentaerythritol phosphate-triphenyl phosphate compound is preferably 1:0.2-0.4:0.2-0.4, and more preferably 3:1:1; the mass ratio of the melamine polyphosphate to the melamine cyanurate to the triphenyl phosphate in the melamine polyphosphate-melamine cyanurate-triphenyl phosphate compound is preferably 1:0.2-0.4:0.2-0.4, and more preferably 3:1:1.
In the present invention, the dispersant is preferably a surfactant, or preferably a mixture of a surfactant and a water-soluble dispersant; in the present invention, the surfactant preferably includes one or more of sulfate, sulfonate, fatty acid salt, sodium fatty alcohol polyoxyethylene ether sulfate and terzorile; the water-soluble dispersing agent preferably comprises one or more of alkyl cellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and alkylphenol ethoxylates; the sulfate is preferably sodium dodecyl sulfate; the sulfonate is preferably one or more of sodium dodecyl benzene sulfonate, disodium monoisodecyl sulfosuccinate, sodium docusate, sodium methyl isobutyl sulfosuccinate, sodium dicyclohexyl sulfosuccinate and disodium octadecyl sulfosuccinamide; the fatty acid salt is preferably one or more of sodium laurate, sodium myristate, sodium palmitate and barium laurate; the alkyl cellulose preferably comprises one or more of hydroxypropyl fibers, methylcellulose, methyl hydroxyethyl fibers, and hydroxyethyl fibers.
In the present invention, the organic solvent preferably includes methylene chloride, acetone, methyl ethyl ketone, benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, butyl acetate, limonene or terpene, more preferably methylene chloride.
In the present invention, the mixing preferably includes: mixing waste polystyrene, a composite halogen-free flame retardant and an organic solvent to obtain a premix of the composite halogen-free flame retardant and the waste polystyrene; mixing a dispersing agent and water to obtain a dispersing agent water solution; adding the dispersant aqueous solution into the premix of the composite halogen-free flame retardant and the waste polystyrene; the mass ratio of the waste polystyrene to the organic solvent is preferably 1:2-10, more preferably 1:3-8; the mass ratio of the waste polystyrene to the composite halogen-free flame retardant is preferably 100:0.5-10, more preferably 100:2-7; when the dispersant is a surfactant, the mass fraction of the dispersant aqueous solution is preferably 0.2 to 4.5%, more preferably 0.5 to 3%; when the dispersant is a mixture of a surfactant and a water-soluble dispersant, the total mass fraction of the surfactant and the water-soluble dispersant in the dispersant aqueous solution is preferably 0.2 to 5%, wherein the mass fraction of the water-soluble dispersant is preferably not more than 0.5%, more preferably 0.1 to 0.4% (the balance being the surfactant); the volume ratio of the dispersant aqueous solution to the premix of the composite halogen-free flame retardant and the waste polystyrene is preferably 2-10:1, more preferably 3-8:1; in the invention, the waste polystyrene and the composite halogen-free flame retardant are preferably added into the organic solvent, and then the obtained mixed liquid is added into a three-neck flask for continuous stirring for 40min, so that the waste polystyrene and the composite halogen-free flame retardant are fully mixed; the dispersant aqueous solution is preferably slowly added into the premix of the composite halogen-free flame retardant and the waste polystyrene, and the specific addition rate is to ensure uniform stirring and dispersion.
After the mixed solution is obtained, the organic solvent in the mixed solution is distilled off under the stirring condition to obtain halogen-free flame-retardant polystyrene beads; in the present invention, the rotation speed of the stirring is preferably 200 to 400rpm, more preferably 250 to 350rpm; the distillation comprises a first-stage distillation and a second-stage distillation which are sequentially carried out; the temperature of the first-stage distillation is preferably the boiling point temperature of the organic solvent, and the heat preservation time is 1-3 h; the temperature of the second-stage distillation is 15-30 ℃ above the boiling point of the organic solvent, more preferably 20 ℃, and the heat preservation time is 0.5-4 h; the temperature rising rate from room temperature to the temperature of the first-stage distillation is preferably 0.5-2 ℃/min; the rate of temperature increase from the temperature of the first-stage distillation to the temperature of the second-stage distillation is preferably 0.2 to 0.5 ℃/min. In a specific embodiment of the present invention, when the organic solvent is dichloromethane, the temperature of the first stage distillation is 40 ℃, and the temperature of the second stage distillation is 60 ℃; according to the invention, through two-stage distillation, the organic solvent in the system can be completely distilled off; according to the invention, an organic solvent in a system is distilled off under a stirring condition, in the process, polystyrene firstly enters an aqueous phase, liquid drops are formed under the action of stirring shearing force, oil-in-water (O/W) emulsion beads can be stabilized under the action of a dispersing agent, then the separation of polystyrene particles and the solvent is realized by distilling off the solvent, and the selected flame retardant is insoluble in water and is compounded with polystyrene to form halogen-free flame-retardant polystyrene beads in the first stage of distillation; the distilled liquid is an organic solvent and can be reused.
After the organic solvent is distilled off, the invention preferably reduces the temperature and discharges the material, and then the obtained material liquid is filtered, washed and dried in sequence to obtain halogen-free flame-retardant polystyrene beads; the invention removes the moisture and the residual methylene dichloride in the beads by drying; the filtrate obtained by filtration is a dispersant aqueous solution, and the dispersant aqueous solution obtained by filtration is preferably recycled.
The invention also provides the halogen-free flame-retardant polystyrene beads prepared by the preparation method of the scheme, and the particle size of the halogen-free flame-retardant polystyrene beads is 0.5-3 mm, preferably 1-1.5 mm. In the specific examples of the present invention, the halogen-free flame retardant polystyrene beads are mainly used for preparing halogen-free flame retardant expandable polystyrene beads, which will be described in detail later.
The invention also provides a preparation method of the halogen-free flame-retardant expandable polystyrene beads, which comprises the following steps:
under a closed condition, mixing the halogen-free flame-retardant polystyrene beads and the surfactant aqueous solution, heating to 85-100 ℃, then adding a physical foaming agent, stirring at a constant temperature for 4-6 hours, and adding an inorganic dispersing agent into the system in the constant temperature stirring process;
And after the constant-temperature stirring is completed, cooling the obtained product feed liquid, and sequentially carrying out solid-liquid separation and drying to obtain the halogen-free flame-retardant expandable polystyrene beads.
Under the airtight condition, the halogen-free flame-retardant polystyrene beads and the aqueous solution of the surfactant are mixed and heated to 85-100 ℃, then the physical foaming agent is added, the constant temperature stirring is carried out for 4-6 hours, and the inorganic dispersing agent is added into the system in the constant temperature stirring process. In the present invention, the mass fraction of the aqueous surfactant solution is preferably 4 to 8%, more preferably 5 to 7%; the mass ratio of the halogen-free flame-retardant polystyrene beads to the surfactant aqueous solution is preferably 1:1-4, more preferably 1:2-3; the optional types of the surfactant are preferably consistent with the above schemes, and are not described in detail herein; the surfactant plays a role of a dispersing agent and can prevent the halogen-free flame-retardant polystyrene beads from being adhered in the heating process. In the present invention, the physical blowing agent preferably includes one or more of propane, butane, pentane, hexane, heptane, petroleum ether, freon 11 or freon 12; the mass of the physical foaming agent is preferably 6-10% of the mass of the halogen-free flame-retardant polystyrene beads, and more preferably 8.5-9.5%; the inorganic dispersant preferably comprises one or more of calcium phosphate, calcium hydroxy phosphate, calcium carbonate, calcium oxalate, barium sulfate, calcium sulfate, zinc oxide, magnesium hydroxide, aluminum hydroxide, bentonite, kaolin, titanium dioxide, graphite and mica; the mass of the inorganic dispersant is preferably 0.1-8% of the mass of water in the system (namely, water introduced in the foaming process), and is preferably 2-4%; according to the invention, the inorganic dispersing agent with a lamellar structure is added, so that the dispersing agent can be attached to the halogen-free flame-retardant polystyrene beads, the foaming agent can reside on the surfaces of the halogen-free flame-retardant polystyrene beads, the foaming agent can be more easily contacted with the halogen-free flame-retardant polystyrene beads, and meanwhile, the dispersing effect can be realized, and the particle adhesion is avoided.
In the invention, the closed condition is preferably provided by a high-pressure reaction kettle, preferably, halogen-free flame-retardant polystyrene beads are firstly added into the high-pressure reaction kettle, then a surfactant aqueous solution is added, then the temperature is raised to 85-100 ℃ under the condition of continuous stirring, preferably to 90-95 ℃, then a foaming agent is added through a liquid charging port of the high-pressure reaction kettle, stirring is continued for 4-6 hours, preferably stirring is continued for 4.5-5.5 hours, and in the process of continuing stirring, an inorganic dispersing agent is added through a solid charging port of the high-pressure reaction kettle; the inorganic dispersing agent is preferably added after stirring for 0.5 to 1 hour at constant temperature, and a charging port of the high-pressure reaction kettle is immediately closed after the inorganic dispersing agent is added; in the present invention, the rotation speed of the stirring condition is preferably 50 to 300rpm, and the heating rate to 85 to 100℃is preferably 0.5 to 1℃per minute.
After constant temperature stirring is completed, the obtained product liquid is cooled and then is subjected to solid-liquid separation and drying in sequence, so that the halogen-free flame-retardant expandable polystyrene beads are obtained. The invention preferably opens the cooling device of the high-pressure reaction kettle in a stirring state, cools to room temperature, and then discharges to perform solid-liquid separation; the method has no special requirement on the specific conditions of drying, and can fully remove the moisture in the wet material obtained by solid-liquid separation; after drying, the invention also preferably carries out cooling, screening and packaging on the dried halogen-free flame-retardant expandable polystyrene beads, thus obtaining the finished product of the halogen-free flame-retardant expandable polystyrene beads with the particle size of 0.5-3 mm.
The invention also provides the halogen-free flame-retardant expandable polystyrene beads prepared by the preparation method, and the particle size of the halogen-free flame-retardant expandable polystyrene beads is 0.5-3 mm, preferably 1-2.5 mm. The application method of the halogen-free flame-retardant expandable polystyrene beads has no special requirement, and in the specific embodiment of the invention, the halogen-free flame-retardant expandable polystyrene beads are preferably prepared into a plate through foaming and molding.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
25g of waste polystyrene, 0.25g of melamine cyanurate and 0.25g of triphenyl phosphate are taken and added into 100g of methylene dichloride to be dissolved to obtain a premix, and the premix is added into a three-neck flask and continuously stirred for 40min to fully mix the waste polystyrene and the flame retardant. Adding 1g of sodium dodecyl sulfate into 100mL of distilled water to obtain a dispersing agent aqueous solution, slowly adding the dispersing agent aqueous solution into a three-neck flask, and mixing with the premix to obtain a mixed solution;
The stirring speed was controlled at 380rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained after filtration is an aqueous solution containing a dispersing agent and can be reused, and the distilled liquid is dichloromethane and can be reused. Fig. 1 is a physical diagram of the halogen-free flame-retardant polystyrene beads prepared in this example, and it can be seen from fig. 1 that the halogen-free flame-retardant polystyrene beads prepared in this invention are spherical particles with uniform particle size and good dispersibility.
Adding the prepared halogen-free flame-retardant polystyrene beads into a reaction kettle, adding 5g of sodium dodecyl benzene sulfonate into 100mL of distilled water to obtain a surfactant aqueous solution, adding the surfactant aqueous solution into the reaction kettle, continuously stirring, controlling the stirring speed to be 200rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 3g of butane into the reaction kettle, keeping constant temperature and stirring for 4 hours, adding 3g of calcium hydroxy phosphate into the reaction kettle in the process, and immediately closing a charging port of the high-pressure reaction kettle after charging; after constant temperature stirring is finished, a cooling device of the reaction kettle is started under the stirring state, the temperature is reduced to room temperature, solid-liquid separation is carried out (the obtained filtrate is a surfactant aqueous solution and can be repeatedly used), the halogen-free flame-retardant expandable polystyrene spherical beads with certain humidity are obtained, and then the halogen-free flame-retardant expandable polystyrene spherical beads are obtained after drying, cooling, screening and packaging.
Uniformly placing the halogen-free flame-retardant expandable polystyrene beads prepared in the embodiment 1 into a mold, heating for 30-50 s through steam, cooling to obtain a halogen-free flame-retardant polystyrene foam board with the same size as the mold, preparing the foam board into a board, and performing performance test according to national standards, wherein specific detection standards and test results are shown in table 1; the particle diameter data in table 1 are the test data of the halogen-free flame retardant polystyrene beads, and other data are the test data after the halogen-free flame retardant expandable polystyrene beads are prepared into a plate, and the subsequent examples are not repeated.
TABLE 1 halogen-free flame retardant Expandable polystyrene beads Performance test data obtained in example 1
Example 2
25g of waste polystyrene, 1.25g of melamine polyphosphate and 0.25g of triphenyl phosphate are taken and added into 100g of dichloromethane to be dissolved to obtain a premix, and the premix is added into a three-neck flask and is continuously stirred for 40min to fully mix the waste polystyrene and the flame retardant. 2g of sodium dodecyl benzene sulfonate is added into 100mL of distilled water to obtain a dispersant aqueous solution, and the dispersant aqueous solution is slowly added into a glass reaction kettle to be mixed with the premix solution to obtain a mixed solution.
The stirring speed was controlled at 300rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 2 is a physical view of the halogen-free flame retardant polystyrene beads prepared in this example.
Adding the prepared halogen-free flame-retardant polystyrene beads into a reaction kettle, adding 8g of sodium dodecyl benzene sulfonate into 100mL of distilled water to obtain a surfactant solution, adding a surfactant aqueous solution into the reaction kettle, continuously stirring, controlling the stirring speed to be 160rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 3g of pentane into the reaction kettle, stirring at a constant temperature for 4 hours, adding 2g of bentonite into the reaction kettle in the process, and immediately closing a feed inlet of the high-pressure reaction kettle after the addition; and (3) starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation (the obtained filtrate is a surfactant aqueous solution and can be reused) to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene beads.
The halogen-free flame retardant expandable polystyrene spherical beads of the embodiment 2 are uniformly placed in a mold, heated for 30-50 s by steam, cooled to obtain a halogen-free flame retardant polystyrene foam board with the same size as the mold, and prepared into a board, and performance test is carried out according to national standards, and specific detection standards and test results are shown in Table 2:
TABLE 2 data for Performance test of halogen-free flame retardant expandable polystyrene beads obtained in example 2
Example 3
300g of waste polystyrene, 9g of hexaphenoxy cyclotriphosphazene, 3g of melamine cyanurate and 3g of triphenyl phosphate are taken and added into 1000g of methylene dichloride to be dissolved to obtain a premix, and the premix is added into a glass reaction kettle to be continuously stirred for 40min, so that the waste polystyrene and the flame retardant are fully mixed. Adding 15g of fatty alcohol polyoxyethylene ether sodium sulfate into 1L of distilled water to obtain a dispersing agent aqueous solution, slowly adding the dispersing agent aqueous solution into a glass reaction kettle, and mixing with the premix to obtain a mixed solution;
the stirring speed was controlled at 380rpm, and the resulting mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 3 is a physical view of the halogen-free flame retardant polystyrene beads prepared in this example.
Adding the prepared halogen-free polystyrene flame-retardant beads into a high-pressure reaction kettle, adding 40g of sodium dodecyl sulfate into 500mL of distilled water to obtain a surfactant aqueous solution, adding the surfactant aqueous solution into the high-pressure reaction kettle, continuously stirring, controlling the stirring speed to be 260rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 30g of freon 11 into the high-pressure reaction kettle, stirring at a constant temperature for 1h, adding 20g of sericite through a charging port of the high-pressure reaction kettle, and immediately closing the charging port of the high-pressure reaction kettle after charging. After the second feeding, keeping constant temperature stirring for 3 hours, starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation (the obtained filtrate is a surfactant aqueous solution and can be reused) to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene beads.
The halogen-free flame retardant expandable polystyrene spherical beads of the embodiment 3 are uniformly placed in a mold, heated for 30-50 s by steam, cooled to obtain a halogen-free flame retardant polystyrene foam board with the same size as the mold, and prepared into a board, and performance test is carried out according to national standards, and specific detection standards and test results are shown in Table 3:
TABLE 3 data for Performance test of halogen-free flame retardant expandable polystyrene beads obtained in example 3
Example 4
300g of waste polystyrene, 9g of ammonium polyphosphate, 3g of tripentaerythritol phosphate and 3g of tricresyl phosphate are taken and added into 1000g of methylene dichloride to be dissolved to obtain a premix, and the premix is added into a glass reaction kettle to be continuously stirred for 40min so as to fully mix the waste polystyrene and the flame retardant. Adding 8g of sodium dodecyl benzene sulfonate and 2g of alkylphenol ethoxylates into 1L of distilled water to obtain a dispersing agent aqueous solution, slowly adding the dispersing agent aqueous solution into a glass reaction kettle, and mixing with the premix to obtain a mixed solution;
the stirring speed was controlled at 400rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 4 is a physical view of the halogen-free flame retardant polystyrene beads prepared in this example.
And adding the halogen-free flame-retardant polystyrene beads prepared in the above way into a high-pressure reaction kettle. Adding 25g of sodium dodecyl benzene sulfonate into 500mL of distilled water to obtain a surfactant aqueous solution, adding the surfactant aqueous solution into a high-pressure reaction kettle, continuously stirring, controlling the stirring speed to be 260rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 30g of butane into the high-pressure reaction kettle, stirring at a constant temperature for 1h, adding 10g of sericite and 10g of talcum powder through a charging port of the high-pressure reaction kettle, and immediately closing the charging port of the high-pressure reaction kettle after charging. After the second feeding, keeping constant temperature stirring for 3 hours, starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene bead products.
The halogen-free flame retardant expandable polystyrene beads of the example 4 are uniformly placed in a mold, heated for 30-50 s by steam, cooled to obtain a halogen-free flame retardant polystyrene foam board with the same size as the mold, and prepared into a board, and performance test is carried out according to national standards, and specific detection standards and test results are shown in Table 4:
TABLE 4 test data on the Performance of halogen-free flame retardant expandable polystyrene beads obtained in example 4
Example 5
3000g of waste polystyrene, 90g of melamine polyphosphate, 30g of melamine cyanurate and 30g of triphenyl phosphate are taken, added into 7500g of methylene dichloride to be dissolved to obtain a premix, and the premix is added into a glass reaction kettle to be continuously stirred for 40min, so that the waste polystyrene and the flame retardant are fully mixed. Adding 100g of sodium dodecyl sulfate and 10g of hydroxypropyl fiber into 5L of distilled water to obtain a dispersing agent aqueous solution, slowly adding the dispersing agent aqueous solution into a glass reaction kettle, and mixing with the premix to obtain a mixed solution;
the stirring speed was controlled at 350rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 5 is a physical view of the halogen-free flame retardant polystyrene beads prepared in this example.
Adding the halogen-free flame-retardant polystyrene beads prepared in the above into a high-pressure reaction kettle, adding 250g of sodium dodecyl benzene sulfonate into 5L of distilled water to obtain a surfactant aqueous solution, adding the surfactant aqueous solution into the high-pressure reaction kettle, continuously stirring, controlling the stirring speed to be 260rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 300g of pentane into the high-pressure reaction kettle, stirring at a constant temperature for 1h, adding 100g of sericite and 100g of calcium hydroxy phosphate through a charging hole of the high-pressure reaction kettle, and immediately closing the charging hole of the high-pressure reaction kettle after charging. After the second feeding, keeping constant temperature stirring for 3 hours, starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene bead products.
The halogen-free flame retardant expandable polystyrene beads of the embodiment 5 are uniformly placed in a mold, heated for 30-50 s through steam, cooled to obtain a halogen-free flame retardant polystyrene foam board with the same size as the mold, and the halogen-free flame retardant polystyrene foam board is prepared into a board, and the performance test is carried out according to national standards, and the specific detection standards and test results are shown in Table 5:
TABLE 5 halogen-free flame retardant Expandable polystyrene beads Performance test data obtained in example 5
Comparative example 1 Using Water-soluble flame retardant
25g of waste polystyrene and 1.5g of ammonium polyphosphate (water-soluble oligomeric ammonium polyphosphate) are taken, added into 100g of methylene dichloride to be dissolved to obtain a premix, and the premix is added into a three-neck flask to be continuously stirred for 40min so as to fully mix the waste polystyrene and the flame retardant. 2g of sodium dodecyl benzene sulfonate is added into 100mL of distilled water to obtain a dispersant aqueous solution, and the dispersant aqueous solution is slowly added into a glass reaction kettle to be mixed with the premix solution to obtain a mixed solution.
The stirring speed was controlled at 300rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 6 is a physical view of the halogen-free flame retardant polystyrene beads prepared in comparative example 1.
Adding the prepared halogen-free flame-retardant polystyrene beads into a reaction kettle, adding 8g of sodium dodecyl benzene sulfonate into 100mL of distilled water to obtain a surfactant solution, adding a surfactant aqueous solution into the reaction kettle, continuously stirring, controlling the stirring speed to be 160rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 3g of pentane into the reaction kettle, stirring at a constant temperature for 4 hours, adding 2g of bentonite into the reaction kettle in the process, and immediately closing a feed inlet of the high-pressure reaction kettle after the addition; and (3) starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation (the obtained filtrate is a surfactant aqueous solution and can be reused) to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene beads.
The halogen-free flame-retardant expandable polystyrene spherical beads of the comparative example 1 are uniformly placed in a mold, heated for 30-50 s by steam, cooled to obtain a halogen-free flame-retardant polystyrene foam board with the same size as the mold, and prepared into a board, and performance test is carried out according to national standards, and specific detection standards and test results are shown in Table 6:
TABLE 6 Performance test data for halogen-free flame retardant expandable polystyrene beads obtained in comparative example 1
Comparative example 2 Single halogen-free flame retardant was used
25g of waste polystyrene and 1.5g of melamine polyphosphate are taken, added into 100g of dichloromethane to be dissolved to obtain a premix, and the premix is added into a three-neck flask to be continuously stirred for 40min so as to fully mix the waste polystyrene and the flame retardant. 2g of sodium dodecyl benzene sulfonate is added into 100mL of distilled water to obtain a dispersant aqueous solution, and the dispersant aqueous solution is slowly added into a glass reaction kettle to be mixed with the premix solution to obtain a mixed solution.
The stirring speed was controlled at 300rpm, and the mixed solution was heated from room temperature, and maintained for 2 hours after the temperature was raised to 40℃at a heating rate of 0.5℃per minute, and maintained for 1 hour after the temperature was raised to 60℃at a heating rate of 0.5℃per minute, to ensure that no more methylene chloride was distilled off. Cooling, discharging, filtering and washing to obtain spherical beads, and drying to remove water and residual dichloromethane in the beads to obtain the halogen-free flame-retardant polystyrene beads. The filtrate obtained by filtration is an aqueous solution containing a dispersing agent, can be reused, and the distilled liquid is dichloromethane or can be reused. FIG. 7 is a physical view of the halogen-free flame retardant polystyrene beads prepared in comparative example 2.
Adding the prepared halogen-free flame-retardant polystyrene beads into a reaction kettle, adding 8g of sodium dodecyl benzene sulfonate into 100mL of distilled water to obtain a surfactant solution, adding a surfactant aqueous solution into the reaction kettle, continuously stirring, controlling the stirring speed to be 160rpm, heating to 90 ℃ at a heating rate of 1 ℃/min, adding 3g of pentane into the reaction kettle, stirring at a constant temperature for 4 hours, adding 2g of bentonite into the reaction kettle in the process, and immediately closing a feed inlet of the high-pressure reaction kettle after the addition; and (3) starting a reaction kettle cooling device under the stirring state, cooling to room temperature, performing solid-liquid separation (the obtained filtrate is a surfactant aqueous solution and can be reused) to obtain halogen-free flame-retardant expandable polystyrene beads with certain humidity, and then drying, cooling, screening and packaging to obtain halogen-free flame-retardant expandable polystyrene beads.
The halogen-free flame-retardant expandable polystyrene spherical beads of the comparative example 2 are uniformly placed in a mold, heated for 30-50 s by steam, cooled to obtain a halogen-free flame-retardant polystyrene foam board with the same size as the mold, and prepared into a board, and performance test is carried out according to national standards, and specific detection standards and test results are shown in Table 7:
TABLE 7 Performance test data for halogen-free flame retardant expandable polystyrene beads obtained in comparative example 2
As can be seen from the results of the examples and comparative examples, the panels produced in the examples all had a burn rating of B 1 Grade, comparative example 1 using water-soluble ammonium oligomeric phosphate as flame retardant, the resulting sheet had a burn grade of B 3 A stage, probably because the flame retardant is easily dissolved in the aqueous phase, and effective compounding with polystyrene cannot be achieved; comparative example 2A single halogen-free flame retardant was used to give a panel of burn rating B 2 A stage.
The results show that the invention prepares the halogen-free flame-retardant polystyrene beads by taking the water-insoluble composite halogen-free flame retardant and the waste polystyrene as raw materials, and prepares the halogen-free flame-retardant expandable polystyrene beads by adding the foaming agent, the obtained product has excellent flame retardant property and can reach B 1 A stage; meanwhile, the water-soluble flame retardant cannot be compounded with polystyrene by the method, and the flame retardant property of the halogen-free flame retardant expandable polystyrene beads prepared by using the compound halogen-free flame retardant is better than that of the halogen-free flame retardant by using a single halogen-free flame retardant. In addition, the invention can realize the high-efficiency recycling of the waste polystyrene, solves the problem of environmental pollution caused by the waste polystyrene, and meanwhile, the halogen-free flame-retardant expandable polystyrene beads prepared by the invention have good flame retardance, and avoid the potential safety hazard problem during the storage of the polystyrene; the preparation method provided by the invention has the advantages of simple process, energy conservation, emission reduction, environment friendliness and wide application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for preparing the halogen-free flame-retardant polystyrene beads by using the waste polystyrene is characterized by comprising the following steps of:
mixing waste polystyrene, a composite halogen-free flame retardant, a dispersing agent, water and an organic solvent to obtain a mixed solution; the compound halogen-free flame retardant is obtained by compounding at least two halogen-free flame retardants; the halogen-free flame retardant is a phosphorus flame retardant, a nitrogen flame retardant or a nitrogen-phosphorus flame retardant; the halogen-free flame retardant is a water-insoluble flame retardant;
and (3) under the stirring condition, evaporating the organic solvent in the mixed solution to obtain the halogen-free flame-retardant polystyrene beads.
2. The method of claim 1, wherein the mixing comprises:
mixing waste polystyrene, a composite halogen-free flame retardant and an organic solvent to obtain a premix of the composite halogen-free flame retardant and the waste polystyrene;
mixing a dispersing agent and water to obtain a dispersing agent water solution;
And adding the dispersant aqueous solution into the premix of the composite halogen-free flame retardant and the waste polystyrene.
3. The method according to claim 2, wherein the mass ratio of the waste polystyrene to the organic solvent is 1:2-10; the mass ratio of the waste polystyrene to the composite halogen-free flame retardant is 100:0.5-10;
the dispersing agent is a surfactant or a mixture of the surfactant and a water-soluble dispersing agent; when the dispersing agent is a surfactant, the mass fraction of the dispersing agent aqueous solution is 0.2-4.5%; when the dispersing agent is a mixture of a surfactant and a water-soluble dispersing agent, the total mass fraction of the surfactant and the water-soluble dispersing agent in the dispersing agent aqueous solution is 0.2-5%, wherein the mass fraction of the water-soluble dispersing agent is less than or equal to 0.5%;
the volume ratio of the dispersant aqueous solution to the premix of the composite halogen-free flame retardant and the waste polystyrene is 2-10:1.
4. The method of claim 1, wherein the composite halogen-free flame retardant comprises at least two of ammonium polyphosphate, hexaphenoxy cyclotriphosphazene, melamine polyphosphate, melamine cyanurate, melamine phytate, tripentaerythritol phosphate, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, tetraethyl N, N-p-phenylenediamine (2-hydroxy) dibenzylphosphonate;
The surfactant comprises one or more of sulfate, sulfonate, fatty acid salt, fatty alcohol polyoxyethylene ether sodium sulfate and terzorile; the water-soluble dispersing agent comprises one or more of alkyl cellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid and alkylphenol ethoxylates;
the organic solvent comprises dichloromethane, acetone, methyl ethyl ketone, benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, butyl acetate, limonene or terpene.
5. The process of claim 1 or 4, wherein the distilling comprises a first stage distillation and a second stage distillation performed sequentially; the temperature of the first-stage distillation is the boiling point temperature of the organic solvent, and the heat preservation time is 1-3 h; the temperature of the second-stage distillation is 15-30 ℃ above the boiling point of the organic solvent, and the heat preservation time is 0.5-4 h; the temperature rising rate from room temperature to the temperature of the first-stage distillation is 0.5-2 ℃/min; the temperature rising rate from the temperature of the first-stage distillation to the temperature of the second-stage distillation is 0.2-0.5 ℃/min.
6. The halogen-free flame retardant polystyrene beads prepared by the method according to any one of claims 1 to 5, wherein the particle size of the halogen-free flame retardant polystyrene beads is 0.5 to 3mm.
7. A method for preparing halogen-free flame-retardant expandable polystyrene beads, which is characterized by comprising the following steps:
mixing the halogen-free flame-retardant polystyrene beads according to claim 6 with the surfactant aqueous solution under a closed condition, heating to 85-100 ℃, adding the physical foaming agent, stirring at constant temperature for 4-6 h, and adding the inorganic dispersing agent into the system in the constant temperature stirring process;
and after the constant-temperature stirring is completed, cooling the obtained product liquid, and sequentially carrying out solid-liquid separation and drying to obtain the halogen-free flame-retardant expandable polystyrene beads.
8. The preparation method according to claim 7, wherein the mass fraction of the aqueous surfactant solution is 4 to 8%; the mass ratio of the halogen-free flame-retardant polystyrene beads to the surfactant aqueous solution is 1:1-4.
9. The method of claim 7, wherein the physical blowing agent comprises one or more of propane, butane, pentane, hexane, heptane, petroleum ether, freon 11, or freon 12; the mass of the physical foaming agent is 6-10% of the mass of the halogen-free flame-retardant polystyrene beads;
the inorganic dispersant comprises one or more of calcium phosphate, calcium hydroxy phosphate, calcium carbonate, calcium oxalate, barium sulfate, calcium sulfate, zinc oxide, magnesium hydroxide, aluminum hydroxide, bentonite, kaolin, titanium dioxide, graphite and mica; the mass of the inorganic dispersant is 0.1-8% of the mass of water in the system.
10. The halogen-free flame-retardant expandable polystyrene beads prepared by the preparation method according to any one of claims 7 to 9, wherein the particle size of the halogen-free flame-retardant expandable polystyrene beads is 0.5 to 3mm.
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CN117682732A (en) * | 2024-02-04 | 2024-03-12 | 佛山市骏虎表面技术有限公司 | Zero-emission treatment method for aluminum processing wastewater |
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CN117682732A (en) * | 2024-02-04 | 2024-03-12 | 佛山市骏虎表面技术有限公司 | Zero-emission treatment method for aluminum processing wastewater |
CN117682732B (en) * | 2024-02-04 | 2024-04-19 | 佛山市骏虎表面技术有限公司 | Zero-emission treatment method for aluminum processing wastewater |
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