CN109897357B - High-stability halogen-free environment-friendly flame retardant for plastics and preparation method thereof - Google Patents
High-stability halogen-free environment-friendly flame retardant for plastics and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-stability halogen-free environment-friendly flame retardant for plastics and a preparation method thereof, wherein the flame retardant is prepared from the following raw materials in parts by weight: 45-80 parts of modified polysiloxane, 20-32 parts of fumed silica, 8-15 parts of modified diatomite, 2-5 parts of surface treating agent and 1-2 parts of polyethylene wax. Compared with the prior art, the flame retardant has good flame-retardant and smoke-suppression effects, is safe and reliable, has wide raw material sources and low cost, does not contain toxic additives, can improve the machining and flame-retardant heat-resistant properties of a base material, has good plasticity, can effectively reduce the smoke generation amount and inhibit the generation of carbon dioxide, and completely meets the environment-friendly requirements of novel flame retardants on no halogen and phosphorus.
Description
Technical Field
The invention belongs to the technical field of flame retardance, and relates to a high-stability halogen-free environment-friendly flame retardant for plastics and a preparation method thereof.
Background
It is well known that plastics as synthetic polymer materials have been widely used in various aspects of human life due to their excellent moldability, film-forming properties, insulating properties, acid and alkali resistance, low air permeability, water permeability, and easy coloring. However, plastics and most high molecular materials are flammable materials, and a large amount of smoke and toxic gas are generated during combustion, so that the environment is polluted, the health of people is seriously harmed, and even people die due to toxicity, which becomes a social problem of increasing attention of people. In order to reduce the fire hazard of plastics in best effort, and therefore how to improve the flame retardancy of plastic materials, the plastic materials are an urgent problem to be solved.
The flame retardant is one of the most important chemical additives and is widely applied to general plastics, engineering plastics, plastic alloys, polyurethane and the like. The halogen-containing flame retardant has the advantages of high flame retardant efficiency, small addition amount and the like, is still widely applied at present, but brings huge environmental protection pressure due to the fact that the halogen-containing flame retardant, particularly the bromine flame retardant, has large smoke generation amount in the combustion process and releases a large amount of toxic and corrosive gas in the combustion process. The organic phosphorus flame retardant is the most important halogen-free flame retardant in the current market, is often used in engineering plastic alloys and polyurethane, and has the advantages of low toxicity, low smoke emission and the like. However, the organic phosphorus flame retardant releases corrosive acidic substances during combustion, so that the organic phosphorus flame retardant has high corrosivity for substrates and surrounding environments, and the flame retardant is required to achieve the flame retardant effect of UL V0, and the addition amount of the flame retardant is required to be more than 10%, so that the heat resistance of the plastic alloy is reduced, the toughness is poor, and the mechanical strength is reduced, so that the application range of the plastic alloy is limited to a certain extent. The inorganic flame retardant has the advantages of low price, flame retardance, smoke abatement and the like, is an environment-friendly flame retardant, and is often used in halogen-free flame-retardant polyolefin. However, the flame retardant has the disadvantage that the flame retardant is required to be added in a large amount, usually more than 50%, to achieve a better flame retardant level, which causes the specific gravity of the plastic to be seriously increased, further loses the advantage of small specific gravity, and simultaneously causes the processing performance to be poor, the toughness to be reduced and further limits the application field of the plastic.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the high-stability halogen-free environment-friendly flame retardant for the plastic, which has good economic practicability and good compatibility and stability with the plastic and can effectively give consideration to the processability and the mechanical property of the plastic.
The invention also aims to provide a preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics.
The purpose of the invention can be realized by the following technical scheme:
the high-stability halogen-free environment-friendly flame retardant for the plastics is prepared from the following raw materials in parts by weight: 45-80 parts of modified polysiloxane, 20-32 parts of fumed silica, 8-15 parts of modified diatomite, 2-5 parts of surface treating agent and 1-2 parts of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 8-12:1, transferring the mixture into a mixer, heating the mixture to 140 ℃ for 120 plus materials, firstly stirring the mixture for 30-50min at the rotating speed of 2000r/min for 1000 plus materials, then adding peroxide with the mass being 1.5-2% of the mass of the polyester resin, then stirring the mixture for 60-75min at the rotating speed of 5000r/min for 4000 plus materials, and naturally cooling the mixture to room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the blend of the amber resin and the polyester resin in an organic solvent, heating to 130-136 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting at constant temperature of 135 ℃ under the pressure of 30-40Mpa for 2-4h, and then decompressing and drying to obtain the modified polyorganosiloxane.
The polyester resin in the step (I) is polytrimethylene terephthalate, and the peroxide is one or more of tert-butyl peroxybenzoate, benzoyl peroxide or lauroyl peroxide.
The concentration of the blend of the amber resin and the polyester resin in the step (II) in the organic solvent is 0.4-0.6g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:0.8-1.2: 10.
The polysiloxane is one or more of polydiethylsiloxane, polydimethylsiloxane or polymethylsiloxane, and the coupling agent is alpha-methacryloyloxymethyl trimethoxysilane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 50-60 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premix liquid I in the step (iii) is 1: 3.
The surface treating agent is one or more of amino silicone oil, hydroxyl silicone oil, diphenyl silanediol or methyl ethoxysilane.
A preparation method of a high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 60-80 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state for multiple times by using a high-pressure atomizing sprayer to prepare a premix;
step (2): at the temperature of 120-160 ℃, in a stirring state, the modified polysiloxane is dripped into the premix according to the weight portion, stirred for 1-3h at constant temperature, then the polyethylene wax is added, stirred and mixed evenly, discharged and dried in vacuum, and the modified polysiloxane is prepared.
In the step (1), the surface treating agent is heated to 90-110 ℃ and then transferred to a high-pressure atomization sprayer.
When the high-stability halogen-free environment-friendly flame retardant for plastics is actually applied, the addition amount of the high-stability halogen-free environment-friendly flame retardant for plastics is 3-10%.
Compared with the prior art, the invention has the following characteristics:
1) the succinic resin is adopted to modify the polyorganosiloxane, active groups can be introduced at the molecular chain terminal or on the side chain, and under the action of the catalyst, the active groups on the polyester resin and the succinic resin molecular chain react with the active groups of the polyorganosiloxane to generate block, graft or interpenetrating network copolymers, so that the copolymer has excellent heat resistance, can effectively improve the compatibility of a flame retardant system and plastic, plays a role in enhancing and toughening, and overcomes the defect that the traditional flame retardant affects the strength and toughness of the plastic;
2) the diatomite is modified jointly by adopting a titanate coupling agent and polyvinyl alcohol, organic groups can be grafted on the surfaces of the diatomite microparticles, the outer surfaces of the diatomite microparticles can be coated with acrylic resin, the dispersibility among the diatomite microparticles can be good, and the phenomenon that the microparticles are agglomerated and settled is prevented, so that the diatomite microparticles not only can play a role of a surfactant and enhance the compatibility between modified polysiloxane and a plastic base material, but also can be used as a reinforcing filler to improve the mechanical strength of the plastic base material, and can be used in combination with fumed silica to realize synergistic interaction, thereby playing roles of isolating oxygen and reducing the surface temperature of the material, effectively retarding flame and suppressing smoke, and greatly improving the flame retardant effect of a flame retardant system;
3) the modified polysiloxane in the flame retardant is combined into a plastic base material structure similar to an Interpenetrating Polymer Network (IPN) partial crosslinking mechanism, can effectively limit the dispersibility and the flowability of the fumed silica and the modified diatomite, prevents the fumed silica and the modified diatomite from migrating to the surface of a flame-retardant polymer, and has excellent flame-retardant stability;
4) the flame retardant disclosed by the invention has the advantages of good flame-retardant and smoke-suppression effects, safety, reliability, wide raw material source, low cost, no toxic additive, capability of improving the machining and flame-retardant heat-resistant properties of a base material, good plasticity, capability of effectively reducing the smoke generation amount and inhibiting the generation of carbon dioxide, and completely accords with the environment-friendly requirements of novel flame retardants on halogen and phosphorus.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 52 parts of modified polysiloxane, 21 parts of fumed silica, 10 parts of modified diatomite, 3 parts of surface treating agent and 1 part of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 9:1, transferring the mixture into a mixer, heating the mixture to 130 ℃, firstly stirring the mixture at the rotating speed of 2000r/min for 40min, then adding peroxide with the mass being 1.6 percent of the mass of the polyester resin, then stirring the mixture at the rotating speed of 4000r/min for 60min, and naturally cooling the mixture to room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 132 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting for 3 hours at a constant temperature of 135 ℃ under the pressure of 32MPa, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate, and the peroxide is tert-butyl peroxybenzoate.
The concentration of the blend of the amber resin and the polyester resin in the organic solvent in the step (II) is 0.5g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:0.8: 10. The polysiloxane is polydiethylsiloxane, and the coupling agent is alpha-methacryloxymethyltrimethoxysilane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 55 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In this example, the surface treatment agent was amino silicone oil.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 70 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 135 ℃, stirring at constant temperature for 2.5h, adding the polyethylene wax, uniformly stirring and mixing, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 95 ℃ and then transferred to a high-pressure atomization sprayer.
Example 2:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 58 parts of modified polysiloxane, 22 parts of fumed silica, 9 parts of modified diatomite, 2 parts of surface treating agent and 1 part of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 8:1, transferring the mixture into a mixer, heating the mixture to 135 ℃, firstly stirring the mixture at the rotating speed of 1800r/min for 45min, then adding peroxide with the mass being 1.7 percent of the mass of the polyester resin, then stirring the mixture at the rotating speed of 4200r/min for 65min, and naturally cooling the mixture to room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 134 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting at constant temperature of 135 ℃ under the pressure of 35Mpa for 3.5h, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate and the peroxide is benzoyl peroxide.
The concentration of the blend of the amber resin and the polyester resin in the organic solvent in the step (II) is 0.48g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:1: 10. The polyorganosiloxane is polydimethylsiloxane, and the coupling agent is alpha-methacryloxymethyltrimethoxysilane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 52 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In this example, the surface treatment agent was a hydroxyl silicone oil.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 72 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 140 ℃, stirring at constant temperature for 2 hours, adding the polyethylene wax, uniformly stirring and mixing, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 98 ℃ and then transferred to a high-pressure atomization sprayer.
Example 3:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 64 parts of modified polysiloxane, 25 parts of fumed silica, 12 parts of modified diatomite, 4 parts of surface treating agent and 1.5 parts of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 10:1, transferring the mixture into a mixer, heating the mixture to 130 ℃, firstly stirring the mixture at the rotating speed of 1500r/min for 40min, then adding peroxide with the mass being 1.8 percent of the mass of the polyester resin, then stirring the mixture at the rotating speed of 4500r/min for 65min, and naturally cooling the mixture to room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 135 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting for 4 hours at a constant temperature of 135 ℃ under the pressure of 36MPa, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate, and the peroxide is lauroyl peroxide.
The concentration of the blend of the amber resin and the polyester resin in the organic solvent in the step (II) is 0.52g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:1.1: 10. The polyorganosiloxane is polymethyl siloxane, and the coupling agent is alpha-methacryloxymethyl trimethoxy silane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 52 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In this embodiment, the surface treatment agent is diphenyl silanediol.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 75 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 150 ℃, stirring at constant temperature for 2 hours, adding the polyethylene wax, stirring and mixing uniformly, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 100 ℃ and then transferred to a high-pressure atomization sprayer.
Example 4:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 45 parts of modified polysiloxane, 20 parts of fumed silica, 8 parts of modified diatomite, 2.8 parts of surface treating agent and 1.2 parts of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 9:1, transferring the mixture into a mixer, heating the mixture to 120 ℃, firstly stirring the mixture for 50min at the rotating speed of 1000r/min, then adding peroxide with the mass being 1.5 percent of the mass of the polyester resin, then stirring the mixture for 75min at the rotating speed of 4000r/min, and naturally cooling the mixture to the room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 130 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting at constant temperature of 135 ℃ under the pressure of 30MPa for 3.5h, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate, and the peroxide is lauroyl peroxide.
The concentration of the blend of the amber resin and the polyester resin in the organic solvent in the step (II) is 0.4g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:0.8: 10. The polysiloxane is polydiethylsiloxane, and the coupling agent is alpha-methacryloxymethyltrimethoxysilane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 52 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In this example, the surface treatment agent was methyl ethoxy silane.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 60 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 120 ℃, stirring for 3 hours at constant temperature, adding the polyethylene wax, stirring and mixing uniformly, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 90 ℃ and then transferred to a high-pressure atomization sprayer.
Example 5:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 80 parts of modified polysiloxane, 32 parts of fumed silica, 15 parts of modified diatomite, 5 parts of surface treating agent and 2 parts of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 12:1, transferring the mixture into a mixer, heating the mixture to 140 ℃, firstly stirring the mixture at the rotating speed of 2000r/min for 30min, then adding peroxide with the mass being 2 percent of the mass of the polyester resin, then stirring the mixture at the rotating speed of 5000r/min for 60min, and naturally cooling the mixture to room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 136 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting for 2 hours at a constant temperature of 135 ℃ under the pressure of 40Mpa, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate, and the peroxide is tert-butyl peroxybenzoate.
The concentration of the blend of the amber resin and the polyester resin in the organic solvent in the step (II) is 0.6g/mL, and the mass ratio of the polysiloxane to the coupling agent to the amber resin is 100:1.2: 10. The polyorganosiloxane is polymethyl siloxane, and the coupling agent is alpha-methacryloxymethyl trimethoxy silane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 52 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In this example, the surface treatment agent was amino silicone oil.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 80 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 160 ℃, stirring at constant temperature for 1h, adding the polyethylene wax, uniformly stirring and mixing, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 110 ℃ and then transferred to a high-pressure atomization sprayer.
Example 6:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 72.4 parts of modified polysiloxane, 26 parts of fumed silica, 10 parts of modified diatomite, 4 parts of surface treating agent and 1.6 parts of polyethylene wax.
The preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 10:1, transferring the mixture into a mixer, heating the mixture to 140 ℃, firstly stirring the mixture at the rotating speed of 2000r/min for 30min, then adding peroxide with the mass being 1.8 percent of the mass of the polyester resin, then stirring the mixture at the rotating speed of 5000r/min for 60min, and naturally cooling the mixture to the room temperature to prepare a blend of the amber resin and the polyester resin;
step (II): dissolving the mixture of the amber resin and the polyester resin in an organic solvent, heating to 135 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting for 3 hours at constant temperature of 135 ℃ under the pressure of 32MPa, and then decompressing and drying to obtain the modified polyorganosiloxane.
In the step (I), the polyester resin is polytrimethylene terephthalate, and the peroxide is prepared by mixing tert-butyl peroxybenzoate and lauroyl peroxide according to the mass ratio of 6: 1.
In the step (II), the concentration of the blend of the amber resin and the polyester resin in the organic solvent is 0.5g/mL, and the mass ratio of the polyorganosiloxane to the coupling agent to the amber resin is 100:1: 10. The polysiloxane is prepared by mixing polydiethylsiloxane, polydimethylsiloxane and polymethylsiloxane according to the mass ratio of 3:5:2, and the coupling agent is alpha-methacryloyloxymethyl trimethoxysilane.
The preparation method of the modified diatomite comprises the following steps:
step (i): adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for 1h at 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 60 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
The mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premixed liquid I in the step (iii) is 1: 3.
In the embodiment, the surface treatment agent is prepared by mixing amino silicone oil and diphenyl silanediol according to the mass ratio of 3: 4.
The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics comprises the following steps:
step (1): adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 75 ℃, and then atomizing the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
step (2): and (2) dropwise adding the modified polysiloxane into the premix according to the weight part under the stirring state at 140 ℃, stirring at constant temperature for 2.5h, adding the polyethylene wax, uniformly stirring and mixing, discharging, and drying in vacuum.
In the step (1), the surface treating agent is heated to 105 ℃, and then transferred to a high-pressure atomization sprayer.
Example 7:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 68 parts of modified polysiloxane, 30 parts of fumed silica, 12 parts of modified diatomite, 3 parts of surface treating agent and 1 part of polyethylene wax.
The rest is the same as example 6.
Example 8:
the high-stability halogen-free environment-friendly flame retardant for the plastic is prepared from the following raw materials in parts by weight: 74 parts of modified polysiloxane, 23 parts of fumed silica, 13 parts of modified diatomite, 5 parts of surface treating agent and 2 parts of polyethylene wax.
The rest is the same as example 6.
Comparative example 1:
in the formulation of this comparative example, a conventional commercially available polyorganosiloxane was used in place of the modified polyorganosiloxane, and the rest was the same as in example 6.
Comparative example 2:
in the formulation of this comparative example, ordinary commercially available diatomaceous earth was used in place of the modified diatomaceous earth, as in example 6.
Comparative example 3:
this comparative example is a commercially available halogen-free flame retardant.
And (3) performance testing:
the test formulation: 72 parts of PC, 23 parts of plasticizer DOP, and 5 parts of flame retardant (examples 1-8 and comparative examples 1-3).
Weighing PC and plasticizer according to the mass ratio of the test formula, respectively adding 5 parts of flame retardant to be tested, mixing for 10min in a small high-speed mixer, extruding and granulating, injection molding to obtain sample strips, and then testing the flame retardant performance and the related mechanical properties, wherein the test results are shown in Table 1.
Table 1: flame retardant property and related mechanical property test results
As can be seen from Table 1, the flame retardant disclosed by the invention is excellent in flame retardant effect, has small influence on the mechanical property of the material, can effectively improve the flame retardance of the material while giving consideration to the mechanical property, and has a good application prospect.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. The high-stability halogen-free environment-friendly flame retardant for plastics is characterized by being prepared from the following raw materials, by weight, 45-80 parts of modified polysiloxane, 20-32 parts of fumed silica, 8-15 parts of modified diatomite, 2-5 parts of a surface treatment agent and 1-2 parts of polyethylene wax;
the preparation method of the modified polyorganosiloxane comprises the following steps:
step (I): uniformly mixing the amber resin and the polyester resin together according to the mass ratio of 8-12:1, transferring the mixture into a mixer, heating the mixture to 140 ℃ for 120-;
step (II): dissolving a blend of the succinic resin and the polyester resin in an organic solvent, heating to 130-136 ℃, adding a catalyst, adding the polyorganosiloxane and the coupling agent, reacting at constant temperature of 135 ℃ under the pressure of 30-40Mpa for 2-4h, and then decompressing and drying to obtain the modified polyorganosiloxane;
the preparation method of the modified diatomite comprises the following steps:
adding a titanate coupling agent into isopropanol, uniformly mixing to obtain a titanate coupling agent isopropanol solution, and then mixing the titanate coupling agent isopropanol solution and polyvinyl alcohol according to the mass ratio of 1:0.4 to obtain a premixed solution I;
step (ii): adding acrylic resin into ethanol, stirring and mixing until the acrylic resin is fully dissolved to prepare a premixed solution II;
step (iii): adding diatomite into the premixed solution I, and stirring at a high speed of 3000 r/min for lh at the temperature of 25 ℃; filtering to retain solid, adding into the premix liquid II, and stirring at 35 deg.C at low speed of 800r/min for 2 h; filtering, washing the solid with 10% sulfuric acid solution to remove impurities, washing with water until the solution system is neutral, filtering, vacuum drying at 50-60 deg.C, and grinding to obtain powder with particle size of 800 mesh and 95%.
2. The high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, wherein the polyester resin in step (I) is polytrimethylene terephthalate, and the peroxide is one or more of tert-butyl peroxybenzoate, benzoyl peroxide or lauroyl peroxide.
3. The high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, wherein the concentration of the blend of the amber resin and the polyester resin in the organic solvent in step (II) is 0.4-0.6g/mL, the mass ratio of the polyorganosiloxane to the coupling agent to the amber resin is 100: 0.8-1.2:10.
4. The high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, wherein the polyorganosiloxane is one or more of polydiethylsiloxane, polydimethylsiloxane or polymethylsiloxane, and the coupling agent is a-methacryloyloxymethyltrimethoxysilane.
5. The high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, wherein the mass ratio of the titanate coupling agent to the isopropanol in the step (I) is 3:8, the mass ratio of the acrylic resin to the ethanol in the step (ii) is 1:6, and the mass ratio of the diatomite to the premix I in the step (iii) is 1: 3.
6. The high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, wherein the surface treatment agent is one or more of amino silicone oil, hydroxy silicone oil, diphenyl silanediol or methyl ethoxysilane.
7. The preparation method of the high-stability halogen-free environment-friendly flame retardant for plastics as claimed in claim 1, characterized in that the method comprises the following steps:
adding the fumed silica and the modified diatomite into a mixer according to the parts by weight, uniformly stirring and mixing at 60-80 ℃, and then atomizing and adding the surface treating agent into the mixture of the fumed silica and the modified diatomite in a stirring state by adopting a high-pressure atomizing sprayer for multiple times to prepare a premix;
and (2) dropwise adding the modified polysiloxane into the premix according to the parts by weight under the stirring state at the temperature of 120-160 ℃, stirring for l-3h at constant temperature, adding the polyethylene wax, uniformly stirring and mixing, discharging, and drying in vacuum.
8. The method for preparing the high-stability halogen-free environment-friendly flame retardant for plastics according to claim 7, wherein in the step (1), the surface treatment agent is heated to 90-110 ℃ and then transferred to a high-pressure atomization sprayer.
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