CN111849105A - Polyphosphazene-boron nitride modified acrylic resin flame retardant material and preparation method thereof - Google Patents
Polyphosphazene-boron nitride modified acrylic resin flame retardant material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of acrylic resin flame retardance, and discloses a polyphosphazene-boron nitride modified acrylic resin flame retardant material which comprises the following formula raw materials and components: acrylic resin, chloroacetyl chloride, aluminum chloride and polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets. According to the polyphosphazene-boron nitride modified acrylic resin flame retardant material, rich amino groups of polyethyleneimine react with epoxy functionalized boron nitride nanosheets, then the materials react with hexachlorocyclotriphosphazene to obtain polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, and finally the materials react with chloroacetylated acrylic resin intermediates to obtain polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, so that the interfacial compatibility of the polyphosphazene and boron nitride nanosheets with acrylic resin is improved, the thermal conductivity and heat resistance of the acrylic resin are improved by the boron nitride nanosheets, and the polyphosphazene serving as a nitrogen-sulfur synergistic flame retardant component endows the acrylic resin with excellent flame retardant performance.
Description
Technical Field
The invention relates to the technical field of acrylic resin flame retardance, in particular to a polyphosphazene-boron nitride modified acrylic resin flame retardant material and a preparation method thereof.
Background
The flame retardant is a functional additive for endowing the polymer material with flame retardancy, and can be divided into an additive flame retardant and a reactive flame retardant, wherein the additive flame retardant is filled into the polymer material by a physical and mechanical mixing method, and mostly influences the mechanical property and the like of the material, while the reactive flame retardant is used as a polymerization reaction monomer and is added into a polymer molecular chain by a chemical covalent bond grafting method, and the reactive flame retardant has the advantages of less influence on the mechanical property and the service performance of the material and lasting flame retardancy.
The acrylic resin is thermoplastic or thermosetting resin prepared by using styrene, acrylic ester and derivatives thereof as polymerization monomers, and the acrylic resin is widely applied to the fields of automobiles, electrical appliances, machinery, buildings and the like, but the traditional acrylic resin has lower glass transition temperature and low thermal stability, and the acrylic resin has poorer flame retardant property and is easy to burn, so that the practical application of the acrylic resin is limited, and the research and development of the acrylic resin with high thermal stability and excellent flame retardant property becomes a research hotspot.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a polyphosphazene-boron nitride modified acrylic resin flame retardant material and a preparation method thereof, and solves the problems of low thermal stability and poor flame retardant property of acrylic resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a polyphosphazene-boron nitride modified acrylic resin flame retardant material comprises the following raw materials and components, wherein the acrylic resin, chloroacetyl chloride, aluminum chloride and polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets are 100:5-15:2-8:20-60 in mass ratio.
Preferably, the styrene monomer content in the acrylic resin is 15-40%.
Preferably, the preparation method of the polyphosphazene-boron nitride modified acrylic resin flame retardant material comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the mixture into an ultrasonic processor, performing ultrasonic dispersion and stripping at 70-90 ℃, adding an epoxy silane coupling agent, placing the mixture into an oil bath pot, heating to 100 ℃ and 110 ℃, stirring at a constant speed for reaction for 5-10 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and drying to prepare the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine into a nitrogen atmosphere, heating to 60-70 ℃, stirring at a constant speed for 20-30h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and a polyethyleneimine modified boron nitride nanosheet into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniform ultrasonic dispersion, continuing ultrasonic dispersion treatment, stirring at a constant speed at room temperature for 4-10h, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheet.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin, chloroacetyl chloride and aluminum chloride in a nitrogen atmosphere, heating to 35-55 ℃, stirring at a constant speed for reaction for 10-20h, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring into a mold, drying and curing to form a film, and thus preparing the polyphosphazene-boron nitride modified acrylic resin flame retardant material.
Preferably, the epoxy silane coupling agent in the step (1) is any one of 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, and the mass ratio of the epoxy silane coupling agent to the nano boron nitride is 1-3: 10.
Preferably, the ultrasonic processor in step (1) includes that inside top is provided with the ultrasonic ware, the inside below of ultrasonic processor is provided with the water bath, water bath inside below is provided with elevating gear, elevating gear includes the base, base top fixedly connected with baffle, baffle fixedly connected with spring rod, spring rod fixedly connected with fixture block, fixture block top fixedly connected with bracing piece, bracing piece fixedly connected with objective table, the objective table top is provided with the reaction bottle.
Preferably, the mass ratio of the epoxy functionalized boron nitride nanosheets to the polyethyleneimine in the step (2) is 10: 0.5-2.
Preferably, the mass ratio of the polyethyleneimine modified boron nitride nanosheets, the hexachlorocyclotriphosphazene and the triethylamine in the step (3) is 100:6-15: 70-180.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the polyphosphazene-boron nitride modified acrylic resin flame retardant material, rich amino groups of polyethyleneimine react with epoxy functionalized boron nitride nanosheets, then the polyethyleneimine reacts with hexachlorocyclotriphosphazene under the action of triethylamine to obtain polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, aluminum chloride is used as a catalyst, chloroacetyl chloride is used as an acylation reagent, chlorine atoms and styrene monomers in acrylic resin perform substitution reaction on para-hydrogen atoms to obtain chloroacetyl acylated acrylic resin intermediates, the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets are used as reactive flame retardants, amino groups of the phosphonitrile grafted polyethyleneimine modified boron nitride nanosheets react with chloroacetyl groups of acrylic resin, the polyphosphazene and the boron nitride nanosheets are covalently grafted into a molecular chain of the acrylic resin, and the interface compatibility of the polyphosphazene and the boron nitride nanosheets and the acrylic resin is improved, the boron nitride nanosheets remarkably improve the thermal conductivity, glass transition temperature and heat resistance of the acrylic resin, and the polyphosphazenes as the nitrogen-sulfur synergistic flame-retardant component endows the acrylic resin with ultrahigh limit oxygen index and excellent flame-retardant property.
Drawings
FIG. 1 is a schematic front view of an ultrasonic processor;
fig. 2 is an enlarged schematic view of the lifting device.
1-an ultrasonic processor; 2-an ultrasonic device; 3-water bath; 4-a base; 5-a baffle plate; 6-a spring rod; 7-a fixture block; 8-a support bar; 9-an object stage; 10-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a polyphosphazene-boron nitride modified acrylic resin flame retardant material comprises the following raw materials and components, wherein acrylic resin with 15-40% of styrene monomer content, chloroacetyl chloride, aluminum chloride and polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets are adopted, and the mass ratio of the raw materials to the components is 100:5-15:2-8: 20-60.
The preparation method of the polyphosphazene-boron nitride modified acrylic resin flame retardant material comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the reaction bottle in an ultrasonic processor, wherein the ultrasonic processor comprises an ultrasonic device arranged above the interior of the ultrasonic processor, a water bath tank arranged below the interior of the ultrasonic processor, a lifting device arranged below the interior of the water bath tank and comprising a base, a baffle is fixedly connected above the base, a spring rod is fixedly connected with the baffle, a clamping block is fixedly connected with the spring rod, a supporting rod is fixedly connected above the clamping block, an objective table is fixedly connected with the supporting rod, the reaction bottle is arranged above the objective table, ultrasonic dispersion and stripping are carried out at 70-90 ℃, then adding an epoxy silane coupling agent which is any one of 3-glycidyl ether oxypropyltrimethoxysilane or 3-glycidyl ether oxypropyltriethoxysilane, and the mass ratio of the epoxy silane coupling agent to the nano boron nitride is 1-3:10, heating the mixture to 110 ℃ in an oil bath, stirring at constant speed for reaction for 5-10h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and drying to obtain the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere at a mass ratio of 10:0.5-2, heating to 60-70 ℃, stirring at a constant speed for reaction for 20-30h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, then adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine, carrying out ultrasonic dispersion treatment, stirring at a constant speed at room temperature for 4-10h for reaction, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin, chloroacetyl chloride and aluminum chloride in a nitrogen atmosphere, heating to 35-55 ℃, stirring at a constant speed for reaction for 10-20h, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring into a mold, drying and curing to form a film, and thus preparing the polyphosphazene-boron nitride modified acrylic resin flame retardant material.
Example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the reaction bottle in an ultrasonic processor, arranging the ultrasonic processor above the ultrasonic processor, arranging a water bath below the ultrasonic processor, arranging a lifting device below the water bath, wherein the lifting device comprises a base, a baffle is fixedly connected above the base, a spring rod is fixedly connected with the baffle, a clamping block is fixedly connected with the spring rod, a supporting rod is fixedly connected above the clamping block, a carrying platform is fixedly connected with the supporting rod, a reaction bottle is arranged above the carrying platform, carrying out ultrasonic dispersion and stripping at 70 ℃, adding 3-glycidyl ether oxypropyl triethoxysilane with a mass ratio of 1:10 to the nano boron nitride, placing the reaction bottle in an oil bath pot, heating to 100 ℃, stirring at constant speed for 5 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol and drying, and preparing the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere with the mass ratio of 10:0.5, heating to 60 ℃, stirring at a constant speed for reaction for 20 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniformly dispersing by ultrasonic, carrying out ultrasonic dispersion treatment, stirring and reacting at a constant speed for 4 hours at room temperature, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin with styrene monomer content of 15%, chloroacetyl chloride and aluminum chloride in a mass ratio of 5:100:2:20 in a nitrogen atmosphere, heating to 35 ℃, stirring at a constant speed for reaction for 10 hours, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring the dichloromethane solvent into a mold, drying and curing to form a film, and thus obtaining the polyphosphazene-boron nitride modified acrylic resin flame retardant material 1.
Example 2
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the mixture into an ultrasonic processor, wherein the ultrasonic processor comprises an ultrasonic device arranged above the inside of the ultrasonic processor, a water bath tank arranged below the inside of the ultrasonic processor, and a lifting device arranged below the inside of the water bath tank, the lifting device comprises a base, a baffle is fixedly connected above the base, a spring rod is fixedly connected with the baffle, a clamping block is fixedly connected with the spring rod, a supporting rod is fixedly connected above the clamping block, a carrying platform is fixedly connected with the supporting rod, a reaction bottle is arranged above the carrying platform, ultrasonic dispersion and stripping are carried out at 90 ℃, then 3-glycidyl ether oxypropyltrimethoxysilane is added, the mass ratio of the 3-glycidyl ether oxypropyltrimethoxysilane to the nano boron nitride is 1.5:10, the mixture is placed into an oil bath and heated to 110 ℃, stirring reaction is carried out at constant speed for 10 hours, the solution is filtered to, and preparing the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere at a mass ratio of 10:1, heating to 70 ℃, stirring at a constant speed for reaction for 30 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniformly dispersing by ultrasonic, carrying out ultrasonic dispersion treatment, stirring and reacting at a constant speed for 10 hours at room temperature, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin with styrene monomer content of 24%, chloroacetyl chloride and aluminum chloride in a mass ratio of 8:100:4:30 in a nitrogen atmosphere, heating to 55 ℃, stirring at a constant speed for reaction for 12 hours, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring the dichloromethane solvent into a mold, drying and curing to form a film, and thus preparing the polyphosphazene-boron nitride modified acrylic resin flame retardant material 2.
Example 3
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the mixture into an ultrasonic processor, wherein the ultrasonic processor comprises an ultrasonic device arranged above the inside of the ultrasonic processor, a water bath tank arranged below the inside of the ultrasonic processor, and a lifting device arranged below the inside of the water bath tank, the lifting device comprises a base, a baffle is fixedly connected above the base, a spring rod is fixedly connected with the baffle, a clamping block is fixedly connected with the spring rod, a supporting rod is fixedly connected above the clamping block, a carrying platform is fixedly connected with the supporting rod, a reaction bottle is arranged above the carrying platform, ultrasonic dispersion and stripping are carried out at 80 ℃, then 3-glycidyl ether oxypropyltrimethoxysilane is added, the mass ratio of the 3-glycidyl ether oxypropyltrimethoxysilane to the nano boron nitride is 2.2:10, the mixture is placed into an oil bath pot to be heated to 105 ℃, stirring reaction is carried out at constant speed for 8 hours, the solution is, and preparing the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere with the mass ratio of 10:1.5, heating to 65 ℃, stirring at a constant speed for reaction for 25 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniformly dispersing by ultrasonic, carrying out ultrasonic dispersion treatment, stirring and reacting at a constant speed for 8 hours at room temperature, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin with the styrene monomer content of 30%, chloroacetyl chloride and aluminum chloride in a mass ratio of 12:100:6:45 in a nitrogen atmosphere, heating to 45 ℃, stirring at a constant speed for reaction for 15 hours, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring the dichloromethane solvent into a mold, drying and curing to form a film, and thus obtaining the polyphosphazene-boron nitride modified acrylic resin flame retardant material 3.
Example 4
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the reaction bottle in an ultrasonic processor, arranging the ultrasonic processor above the ultrasonic processor, arranging a water bath below the ultrasonic processor, arranging a lifting device below the water bath, wherein the lifting device comprises a base, a baffle is fixedly connected above the base, a spring rod is fixedly connected with the baffle, a clamping block is fixedly connected with the spring rod, a supporting rod is fixedly connected above the clamping block, a carrying platform is fixedly connected with the supporting rod, a reaction bottle is arranged above the carrying platform, performing ultrasonic dispersion and stripping at 90 ℃, adding 3-glycidyl ether oxypropyl triethoxysilane with a mass ratio of 3:10 to the nano boron nitride, placing the reaction bottle in an oil bath pot, heating to 110 ℃, stirring at constant speed for 6 hours, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol and drying, and preparing the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere at a mass ratio of 10:2, heating to 70 ℃, stirring at a constant speed for reaction for 30 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniformly dispersing by ultrasonic, carrying out ultrasonic dispersion treatment, stirring and reacting at a constant speed for 10 hours at room temperature, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin with the styrene monomer content of 40%, chloroacetyl chloride and aluminum chloride in a mass ratio of 15:100:8:60 in a nitrogen atmosphere, heating to 55 ℃, stirring at a constant speed for reaction for 20 hours, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring the dichloromethane solvent into a mold, drying and curing to form a film, and thus obtaining the polyphosphazene-boron nitride modified acrylic resin flame retardant material 4.
Comparative example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, adding nano boron nitride, placing the mixture into an ultrasonic processor, wherein the ultrasonic processor comprises an ultrasonic device arranged above the inside of the ultrasonic processor, a water bath tank arranged below the inside of the ultrasonic processor, a lifting device arranged below the inside of the water bath tank and comprising a base, a baffle plate fixedly connected above the base and a spring rod fixedly connected with a clamping block, a supporting rod fixedly connected above the clamping block and an objective table fixedly connected above the supporting rod, the reaction bottle is arranged above the objective table, ultrasonic dispersion and stripping are carried out at 90 ℃, then 3-glycidyl ether oxypropyltrimethoxysilane is added, the mass ratio of the 3-glycidyl ether oxypropyltrimethoxysilane to the nano boron nitride is 0.5:10, the mixture is placed into an oil bath pot and heated to 110 ℃, stirring reaction is carried out at constant speed 8, the solution is filtered to remove the solvent, the solid product is washed by using distilled water and ethanol and dried, and preparing the epoxy functionalized boron nitride nanosheet.
(2) Adding a trichloromethane solvent and epoxy functionalized boron nitride nanosheets into a reaction bottle, ultrasonically dispersing uniformly, adding polyethyleneimine in a nitrogen atmosphere with the mass ratio of 10:3, heating to 70 ℃, stirring at a constant speed for reaction for 30 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and ethanol, and drying to prepare the polyethyleneimine modified boron nitride nanosheets.
(3) Adding an acetonitrile solvent and polyethyleneimine modified boron nitride nanosheets into a reaction bottle, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine after uniformly dispersing by ultrasonic, carrying out ultrasonic dispersion treatment, stirring and reacting at a constant speed for 10 hours at room temperature, carrying out reduced pressure distillation, washing and drying on the solution, and preparing the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets.
(4) Adding a dichloromethane solvent into a reaction bottle, adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets, ultrasonically dispersing uniformly, adding acrylic resin with the styrene monomer content of 10%, chloroacetyl chloride and aluminum chloride in a mass ratio of 25:100:10:15 in a nitrogen atmosphere, heating to 55 ℃, stirring at a constant speed for reaction for 20 hours, centrifugally separating and washing the solution by using distilled water and ethanol until the upper layer is clear, dissolving a solid mixed product in the dichloromethane solvent, pouring the dichloromethane solvent into a mold, drying and curing to form a film, and thus obtaining the polyphosphazene-boron nitride modified acrylic resin comparative flame retardant material 1.
The glass transition temperature of the polyphosphazene-boron nitride modified acrylic resin materials in the examples and the comparative examples is tested by using an ATS-TGA-01 thermogravimetric analyzer, and the test standard is GB/T27816-.
The limit oxygen indexes of the polyphosphazene-boron nitride modified acrylic resin materials in the examples and the comparative examples are tested by using a YZS-10A type full-automatic high-precision oxygen index tester, and the test standards are GB/T25264-2010 and GB/T2406-1993.
Claims (7)
1. The polyphosphazene-boron nitride modified acrylic resin flame retardant material is characterized in that: the boron nitride nano-sheet material comprises the following raw materials and components, wherein the raw materials comprise acrylic resin, chloroacetyl chloride, aluminum chloride and polyphosphazene grafted polyethyleneimine modified boron nitride nano-sheet, and the mass ratio of the raw materials to the components is 100:5-15:2-8: 20-60.
2. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 1, wherein: the styrene monomer content in the acrylic resin is 15-40%.
3. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 1, wherein: the preparation method of the polyphosphazene-boron nitride modified acrylic resin flame retardant material comprises the following steps:
(1) adding nano boron nitride into a mixed solvent of distilled water and ethanol, placing the mixture into an ultrasonic processor, performing ultrasonic dispersion and stripping at 70-90 ℃, adding an epoxy silane coupling agent, placing the mixture into an oil bath pot, heating to 110 ℃ for reaction at 100 ℃, reacting for 5-10h, filtering, washing and drying to prepare the epoxy functionalized boron nitride nanosheet;
(2) adding epoxy functionalized boron nitride nanosheets into a trichloromethane solvent, ultrasonically dispersing uniformly, adding polyethyleneimine into a nitrogen atmosphere, heating to 60-70 ℃, reacting for 20-30h, carrying out reduced pressure distillation, washing and drying to prepare polyethyleneimine modified boron nitride nanosheets;
(3) adding a polyethyleneimine modified boron nitride nanosheet into an acetonitrile solvent, uniformly dispersing by ultrasonic, adding an acetonitrile solution of hexachlorocyclotriphosphazene and triethylamine, continuing to perform ultrasonic dispersion treatment, reacting at room temperature for 4-10h, performing reduced pressure distillation, washing and drying to prepare the polyphosphazene grafted polyethyleneimine modified boron nitride nanosheet;
(4) adding polyphosphazene grafted polyethyleneimine modified boron nitride nanosheets into a dichloromethane solvent, ultrasonically dispersing uniformly, adding acrylic resin, chloroacetyl chloride and aluminum chloride into a nitrogen atmosphere, heating to 35-55 ℃, reacting for 10-20h, centrifugally separating and washing, dissolving a solid mixed product into the dichloromethane solvent, pouring into a mold, drying and curing to form a film, and preparing the polyphosphazene-boron nitride modified acrylic resin flame retardant material.
4. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 3, wherein: the epoxy silane coupling agent in the step (1) is any one of 3-glycidyl ether oxypropyl trimethoxysilane or 3-glycidyl ether oxypropyl triethoxysilane, and the mass ratio of the epoxy silane coupling agent to the nano boron nitride is 1-3: 10.
5. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 3, wherein: the ultrasonic processor in step (1) includes that inside top is provided with the ultrasonic ware, the inside below of ultrasonic processor is provided with the water bath, and water bath inside below is provided with elevating gear, and elevating gear includes the base, base top fixedly connected with baffle, baffle fixedly connected with spring beam, spring beam fixedly connected with fixture block, fixture block top fixedly connected with bracing piece, bracing piece fixedly connected with objective table, the objective table top is provided with the reaction bottle.
6. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 3, wherein: the mass ratio of the epoxy functionalized boron nitride nanosheet to the polyethyleneimine in the step (2) is 10: 0.5-2.
7. The polyphosphazene-boron nitride modified acrylic resin flame retardant material as claimed in claim 3, wherein: the mass ratio of the polyethyleneimine modified boron nitride nanosheet, the hexachlorocyclotriphosphazene and the triethylamine in the step (3) is 100:6-15: 70-180.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112812574A (en) * | 2020-12-31 | 2021-05-18 | 宁波伟裕工贸有限公司 | Preparation method of high-thermal-conductivity boron nitride modified styrene butadiene rubber |
| CN113957728A (en) * | 2021-11-29 | 2022-01-21 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
| CN114645451A (en) * | 2022-04-25 | 2022-06-21 | 中国科学院兰州化学物理研究所 | Layered composite material and preparation method thereof, self-lubricating fiber fabric composite material and preparation method and application thereof |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812574A (en) * | 2020-12-31 | 2021-05-18 | 宁波伟裕工贸有限公司 | Preparation method of high-thermal-conductivity boron nitride modified styrene butadiene rubber |
| CN113957728A (en) * | 2021-11-29 | 2022-01-21 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
| CN113957728B (en) * | 2021-11-29 | 2024-03-26 | 广东昊天服装实业有限公司 | Preparation method and application of nanogel composite dyeing flame retardant |
| CN114645451A (en) * | 2022-04-25 | 2022-06-21 | 中国科学院兰州化学物理研究所 | Layered composite material and preparation method thereof, self-lubricating fiber fabric composite material and preparation method and application thereof |
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